CA3220621A1 - Herbicide composition and process for preparing thereof - Google Patents
Herbicide composition and process for preparing thereof Download PDFInfo
- Publication number
- CA3220621A1 CA3220621A1 CA3220621A CA3220621A CA3220621A1 CA 3220621 A1 CA3220621 A1 CA 3220621A1 CA 3220621 A CA3220621 A CA 3220621A CA 3220621 A CA3220621 A CA 3220621A CA 3220621 A1 CA3220621 A1 CA 3220621A1
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- clodinafop
- propargyl
- metribuzin
- metsulfuron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 207
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 90
- 239000004009 herbicide Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- JBDHZKLJNAIJNC-LLVKDONJSA-N clodinafop-propargyl Chemical group C1=CC(O[C@H](C)C(=O)OCC#C)=CC=C1OC1=NC=C(Cl)C=C1F JBDHZKLJNAIJNC-LLVKDONJSA-N 0.000 claims abstract description 151
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000005583 Metribuzin Substances 0.000 claims abstract description 144
- 239000005584 Metsulfuron-methyl Substances 0.000 claims abstract description 128
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000004563 wettable powder Substances 0.000 claims description 120
- 239000004533 oil dispersion Substances 0.000 claims description 77
- 238000009472 formulation Methods 0.000 claims description 72
- 239000004562 water dispersible granule Substances 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- -1 safeners Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000008187 granular material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- NDQZMBNEHYSVPL-UHFFFAOYSA-N methyl 2-(5-chloroquinolin-8-yl)oxyacetate Chemical group C1=CN=C2C(OCC(=O)OC)=CC=C(Cl)C2=C1 NDQZMBNEHYSVPL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000003002 pH adjusting agent Substances 0.000 claims description 13
- 239000000080 wetting agent Substances 0.000 claims description 13
- 239000006254 rheological additive Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000004530 micro-emulsion Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000004495 emulsifiable concentrate Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000002689 soil Substances 0.000 claims description 9
- 230000007480 spreading Effects 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004491 dispersible concentrate Substances 0.000 claims description 8
- 239000004492 dustable powder Substances 0.000 claims description 8
- 239000004503 fine granule Substances 0.000 claims description 8
- 239000004531 microgranule Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004546 suspension concentrate Substances 0.000 claims description 8
- 239000004548 suspo-emulsion Substances 0.000 claims description 8
- 239000004565 water dispersible tablet Substances 0.000 claims description 8
- 239000005909 Kieselgur Substances 0.000 claims description 7
- 239000003905 agrochemical Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 7
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 150000003871 sulfonates Chemical class 0.000 claims description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 7
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 7
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 229960004249 sodium acetate Drugs 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229960000892 attapulgite Drugs 0.000 claims description 5
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 229940092782 bentonite Drugs 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000004487 encapsulated granule Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000009969 flowable effect Effects 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000004515 macrogranule Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 4
- 239000004550 soluble concentrate Substances 0.000 claims description 4
- 150000003626 triacylglycerols Chemical class 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 239000004549 water soluble granule Substances 0.000 claims description 4
- 239000004552 water soluble powder Substances 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- OPGCOAPTHCZZIW-UHFFFAOYSA-N diethyl 1-(2,4-dichlorophenyl)-5-methyl-4h-pyrazole-3,5-dicarboxylate Chemical group CCOC(=O)C1(C)CC(C(=O)OCC)=NN1C1=CC=C(Cl)C=C1Cl OPGCOAPTHCZZIW-UHFFFAOYSA-N 0.000 claims description 3
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 3
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229940079868 disodium laureth sulfosuccinate Drugs 0.000 claims description 3
- YGAXLGGEEQLLKV-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-2-sulfonatobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)CC(C([O-])=O)S([O-])(=O)=O YGAXLGGEEQLLKV-UHFFFAOYSA-L 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 239000003337 fertilizer Substances 0.000 claims description 3
- 239000000417 fungicide Substances 0.000 claims description 3
- 239000003102 growth factor Substances 0.000 claims description 3
- 239000002917 insecticide Substances 0.000 claims description 3
- 229920005610 lignin Chemical class 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 239000005645 nematicide Substances 0.000 claims description 3
- WQIJVELWNBSHCE-UHFFFAOYSA-N phenyl naphthalene-1-sulfonate Chemical class C=1C=CC2=CC=CC=C2C=1S(=O)(=O)OC1=CC=CC=C1 WQIJVELWNBSHCE-UHFFFAOYSA-N 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
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- 229940001593 sodium carbonate Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
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- 239000004711 α-olefin Substances 0.000 claims description 3
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical class [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
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- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
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- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
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- IZWPGJFSBABFGL-GMFCBQQYSA-M sodium;2-[methyl-[(z)-octadec-9-enoyl]amino]ethanesulfonate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CCS([O-])(=O)=O IZWPGJFSBABFGL-GMFCBQQYSA-M 0.000 claims description 2
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 claims description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 2
- YQWMYVCDMHJIML-UHFFFAOYSA-N S(=O)(=O)(O)C(C(=O)O)CC(=O)O.C(CCCCCCC(C)C)[Na] Chemical compound S(=O)(=O)(O)C(C(=O)O)CC(=O)O.C(CCCCCCC(C)C)[Na] YQWMYVCDMHJIML-UHFFFAOYSA-N 0.000 claims 1
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- 241000196324 Embryophyta Species 0.000 abstract description 99
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present disclosure provides a herbicide composition comprising combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin. The present invention also provides a process for preparing the herbicide composition. The herbicide composition is stable and exhibits a synergistic herbicidal activity in controlling broad spectrum of weeds as such broadleaf weeds and grass weeds in wheat.
Description
HERBICIDE COMPOSITION AND PROCESS FOR PREPARING
THEREOF
FIELD OF THE INVENTION
[0001] The present invention relates to a herbicide composition and a process for preparing the same.
BACKGROUND OF THE INVENTION
THEREOF
FIELD OF THE INVENTION
[0001] The present invention relates to a herbicide composition and a process for preparing the same.
BACKGROUND OF THE INVENTION
[0002] The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] Protection of crops from weeds and other vegetation which inhibit crop growth is a constantly recurring problem in agriculture. To address this problem, researchers are trying to produce an extensive variety of active agents and active agent formulations effective in the control of such undesirable plant growth. Chemical herbicides of many types have been disclosed in the art and a large number are in commercial use. In crop protection, it is desirable in principle to increase specificity and reliability of action of herbicidal active agents. In particular, it is desirable for a crop protection product to control undesirable plants effectively and, at the same time, to be tolerated by useful plants in question.
[0004] Metsulfuron-methyl, Clodinafop-propargyl, Metribuzin are compounds known to be herbicidally active and to be of use in the control of undesirable vegetation, for example in the protection of a range of crops. The herbicides metsulfuron-methyl, clodinafop-propargyl, and metribuzin are independently known in the art for their herbicidal potency. They are disclosed in 'The Pesticide Manual' 15th Edition, published 2009 by the British Crop Protection Council, and are also commercially available.
[0005] Although metsulfuron-methyl, clodinafop-propargyl, and metribuzin are herbicidally active, in many cases they do not provide sufficient control of relevant haimful plants and the activities at low application rates are not always satisfactory. The recommended level of herbicide that may be applied per unit of area is under pressure from governmental, as well as for economic and environmental reasons.
[0006] Further, certain species of undesirable broadleaf weeds and grassy weeds are becoming more and more resistant to a number of most widely used herbicides. Thus, on one hand ever more stringent conditions are being placed on the type and use rate of herbicides, while on the other hand approved herbicides are becoming less and less effective over time in certain species of undesirable plants.
[0007] Furthermore, it is very expensive and time consuming to seek and obtain registration of a new herbicidal compound, including its proposed use rate. Approval data required must not only include evidence of efficacy at the application rates proposed but also safety of herbicide when applied at the recommended level.
[0008] Accordingly, demonstration of synergism by combination of existing herbicidal agents, permits use of individual agents of synergistic combination at lower rates than when used alone, and in many instances ameliorates increasing resistance to herbicidal effectiveness.
[0009] Thus, there is a great need in the art for stable herbicidal composition which reduces dosage of herbicidal agents necessary to obtain acceptable weed control and a process for preparing the herbicidal composition.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0010] The present invention provides a herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin.
[0011] The herbicide composition comprises metsulfuron-methyl in an amount of from 0.01% to 10 % w/w, clodinafop-propargyl in an amount of from 0.1% to 25% w/w and metribuzin in an amount of from 1.0% to 60%
w/w.
w/w.
[0012] The herbicide composition of the present invention is formulated in a number of ways for suitable application. Examples of suitable formulations include water-dispersible granule (WDG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), a flowable suspension (FS), a suspoemulsion (SE), ZC formulation (ZC), soil applied granules (SAG), dustable powder (DP), a gel, a water-dispersible tablet (WT), a dispersible concentrate (DC), an oil-dispersion (OD) or a microencapsulated suspension (CS).
[0013] The herbicide composition of the present invention is preferably formulated as an oil-dispersion (OD), a wettable powder (WP) and a water-dispersible granule (WDG).
[0014] The present invention provides a process for preparing the herbicide composition. The process comprises mixing metsulfuron-methyl, clodinafop-propargyl and metribuzin.
[0015] Preferably, the present invention provides a process for preparing oil-dispersion (OD), a wettable powder (WP) and a water-dispersible granule (WDG) formulation.
[0016] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.
DETAILED DESCRIPTION OF THE INVENTION
DETAILED DESCRIPTION OF THE INVENTION
[0017] The following is a detailed description of embodiments of the present disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0018] Unless the context requires otherwise, throughout the specification which follow, the word "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense that is as "including, but not limited to."
[0019] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0020] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.
[0021] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, process conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about."
Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
[0022] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.
[0023] All methods described herein is performed in suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. "such as") provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0024] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0025] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0026] Various terms are used herein. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that tenn as reflected in printed publications and issued patents at the time of filing.
[0027] The term "herbicide" as used herein, refers to a compound that controls growth of undesirable vegetation.
[0028] As used herein, the term "locus" includes not only areas where weeds may already be growing, but also areas where weeds are yet to emerge, and also areas under cultivation.
[0029] The term "plant" refers to all physical parts of a plant, including shoots, leaves, needles, stalks, stems, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
[0030] As used herein, the phrase "inactive excipients" means excipients which are known and accepted in the art for formation of formulations for agricultural or horticultural use.
[0031] As used herein, the term "pre-emergence" refers to application of the herbicide composition to a habitat, a weed, or soil, prior to emergence of weeds from a soil surface.
[0032] As used herein, the term "post-emergence," refers to application of the herbicide composition to weeds that have already emerged from a soil surface.
[0033] As employed herein, the term "undesirable vegetation" denotes non-crop plant species that otherwise tend to grow in areas where crops are planted, and includes both volunteer crops and weeds. The weeds include broadleaf weeds and grassy weeds.
[0034] The term "control of undesirable vegetation" refers to interference with normal growth and development of undesired vegetation. Examples of control of undesirable vegetation include, but not limited to, inhibition of root growth, inhibition of shoot growth, inhibition of shoot emergence, inhibition of seed production, or reduction of weed biomass.
[0035] The present invention does not use any 'biological materials' that is the materials which are capable of reproducing itself or being reproduced in a biological system.
[0036] The present disclosure provides a herbicide composition comprising combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin.
[0037] Metsulfuron-methyl chemically known as methyl 24[[[(4-methoxy-6-methyl - 1,3,5 -triazin-2-yl)amino] carbonyl] amino] sulfonyllbenzoate is a triazinylsulfonylurea herbicide. It is a selective pre-emergence and post-emergence herbicide used for the control of wide range of broad-leaved weeds in wheat, barley and rice. It acts by inhibiting acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS).
[0038] Clodinafop-propargyl chemically known as 2-propynyl (2R)-2444(5-chloro-3 -fluoro-2-pyridinyl)oxy] phenoxy] propanoate is a aryloxyphenoxypropionic herbicide. It is a selective systemic post emergence herbicide used for the control of grassy weeds in cereals mainly wheat. It acts by inhibition of acetyl CoA carboxylase.
[0039] Metribuzin chemically known as 4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one is a triazinone herbicide. It is a selective pre-emergence and post-emergence herbicide used for controlling broadleaved weeds and annual grasses in crops like sugarcane, wheat and soyabean. It acts by inhibiting photosynthesis by disrupting photo system II in plants.
[0040] The present invention is based upon a surprising finding that metsulfuron-methyl, clodinafop-propargyl, and metribuzin display a synergistic herbicidal effect in the control of undesirable vegetation when applied in combination comprising all three compounds. The synergistic effects allow a reduction in application rate of individual active ingredients, a faster onset of herbicidal action, a longer-lasting action, better control of undesirable vegetation with only one or a few applications, and a broadening of possible application period.
[0041] The synergistic effects of the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin will provide one or more of a number of advantages over the use of each active ingredient alone. In particular, the rates of application of each active ingredient is markedly reduced, when the three compounds are used in combination, while maintaining a high level of herbicidal efficacy. More especially, the use of the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin has the potential to control weed species at a low application rate, in particular at a rate of application at which the individual active ingredients alone are ineffective.
A
treatment using the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin exhibit a considerably broader weed spectrum than the compounds when used alone. The use of a composition comprising the three aforementioned active ingredients also has a speed of action which is faster than that which would have been predicted from the speed of each ingredient used individually and in combination of two ingredients.
A
treatment using the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin exhibit a considerably broader weed spectrum than the compounds when used alone. The use of a composition comprising the three aforementioned active ingredients also has a speed of action which is faster than that which would have been predicted from the speed of each ingredient used individually and in combination of two ingredients.
[0042] The herbicide composition according to the present disclosure is advantageous in the protection of cereal crops, preferably wheat crop.
[0043] The herbicide composition of the present disclosure is useful for post-emergence control of undesirable vegetation. The undesirable vegetation whose control is of greatest interest in the practice of present invention are weeds, and primarily those weeds associated with wheat. The control of undesirable vegetation in wheat is achieved by applying to the undesirable vegetation or to locus of the vegetation the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin in suitable amounts.
[0044] In various embodiments, effective herbicidal effect is achieved with post-emergence application of the herbicide composition of the present disclosure. Useful methods of application include broadcast or localized spraying, drip irrigation or other forms of irrigation, and any of these methods followed by soil tilling. The application rates of the herbicide composition to soil vary over a wide range. The optimal application rates will depend on the crop to be protected, the stage of growth of the crop and of the weed, and the manner in which application is made, i.e., whether by spraying, irrigation, or other means. The total application rate of metsulfuron-methyl, clodinafop-propargyl and metribuzin vary within a wide range, for example from 1 to 2000g per hectare (g/ha). Preferably, the application rate ranges from 20 to 1000 g/ha.
[0045] According to embodiments, the herbicide composition disclosed herein is applied in a single treatment or in several treatments (sequential application), for example by one or more post-emergence applications or one or more early post-emergence applications, and/or followed by one or more applications at medium or late post-emergence.
[0046] The active ingredients metsulfuron-methyl, clodinafop-propargyl and metribuzin are present in the composition in a wide range of amounts. In preferred embodiments, the total amount of metsulfuron-methyl, clodinafop-propargyl and metribuzin in the composition range from 0.1% to 95% by weight of the composition. In some preferred embodiments, the composition comprises, by weight, from 0.01-10% w/w of metsulfuron-methyl, from 0.1 ¨
25% of clodinafop-propargyl and from 1.0 ¨ 60.0 % w/w of metribuzin.
25% of clodinafop-propargyl and from 1.0 ¨ 60.0 % w/w of metribuzin.
[0047] The herbicide composition of the present disclosure is formulated in conventional manner, for example by mixing metsulfuron-methyl, clodinafop-propargyl and metribuzin with one or more inactive excipients. Suitable excipients will depend upon such factors as the type of formulation and the manner of the end use of the formulation, and will be known to a person skilled in the art. In some preferred embodiments, the one or more inactive excipients are selected from anti-crystalline agent, an emulsifier, a wetting agent, a pH modifier, rheology modifier, a solvent, a spreading agent, a dispersing agent, an inert carrier, a stabilizing agent, an anti-caking agent, an anti-foaming agent, an antioxidant or an anti-freezing agent.
[0048] The anti-crystalline agent is selected from vinyl pyrrolidone polymer, calcium salts of (linear and branched) alkyl benzene sulfonic acid or sodium salt of lignosulfonate. The anti-crystalline agent is present in an amount of from 0.1% to 5% by weight based on a total weight of the composition.
[0049] Suitable emulsifier for use in the composition include all substances which normally be used for this purpose in agrochemical compositions.
Examples include substances which are non-ionic, cationic and/or anionic in nature. Suitable emulsifiers include, but not limited to, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyl taurates, and phosphoric esters of polyethoxylated phenols or alcohols, ethoxylated ricinoleic acid triglycerides, castor oil ethoxylate, tristyryphenol ethoxylate or ethoxylated propoxylated polyarylphenol. The emulsifier is present in an amount of from 1% to 12% by weight based on a total weight of the composition.
Examples include substances which are non-ionic, cationic and/or anionic in nature. Suitable emulsifiers include, but not limited to, salts of polyacrylic acids, salts of lignosulphonic acid, salts of phenylsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulphosuccinic ester salts, taurine derivatives, especially alkyl taurates, and phosphoric esters of polyethoxylated phenols or alcohols, ethoxylated ricinoleic acid triglycerides, castor oil ethoxylate, tristyryphenol ethoxylate or ethoxylated propoxylated polyarylphenol. The emulsifier is present in an amount of from 1% to 12% by weight based on a total weight of the composition.
[0050] The wetting agent is selected from alkyl phenol ethoxylate, fatty oil ethoxylate, phenyl naphthalene sulphonates, alkyl naphthalene sulfonates, sodium alkyl naphthalene sulfonate, sodium salt of sulfonated alkyl carboxylate, dioctyl sulfosuccinate sodium salt, polyoxyalkylated ethyl phenols, polyoxyethoxylated fatty alcohols, polyoxyethoxylated fatty amines, lignin derivatives, alkane sulfonates, alpha olefin sulfonates, alkylbenzene sulfonates, salts of polycarboxylic acids, salts of esters of sulfosuccinic acid, octyl phenol ether sulphate, anionic phosphate esters, disodium laureth sulfosuccinate, diisodecyl sodium sulfosuccinate, alkylnaphthalenesulfonates, alkylbenzenesulfonates, alkylpolyglycol ether sulfonates, alkyl ether phosphates, alkyl ether sulfates and alkyl sulfosuccinic monoesters, and mixtures thereof The wetting agent is present in an amount of from 0.1% to 8% by weight based on a total weight of the composition.
[0051] The pH modifier is selected from sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate, dimethyl adipate and mixtures thereof The pH modifier is present in an amount of from 0.01% to 4% by weight based on a total weight of the composition.
[0052] The rheology modifier is selected from hydrophobic silica, fume silica, bentonite, diatomaceous earth, montmorillonite, attapulgites or hydroxymethyl cellulose, xanthan gum, polyvinyl alcohol, cellulose and its derivatives, hydrated clay minerals, magnesium aluminium silicates and mixtures thereof The rheology modifier is present in an amount of from 0.1% to 8% by weight based on a total weight of the composition.
[0053] Suitable solvents for use in the composition is selected from all customary organic solvents which dissolve one or more of the active ingredients employed. Suitable organic solvents for the compounds metsulfuron-methyl, clodinafop-propargyl and metribuzin are known in the art. Preferred solvents include, but not limited to, deionized (DI) water, vegetable oils, methylated vegetable oils, oil medium selected from the group comprising, esterified fatty acids selected from methyl ester of triglycerides containing C12 ¨C22 saturated and unsaturated fatty acids, ethyl ester of triglycerides containing C12 -C22 saturated and unsaturated fatty acids such as methyl soyate, ethyl soyate, rapeseed methyl ester, rapeseed ethyl ester, bio-diesels, paraffinic oil or tall oil. The solvent is present in an amount of from 10% to 90% by weight based on a total weight of the composition.
[0054] Suitable spreading agents are selected from the group comprising of polyoxyethylene alkyl ether, trisiloxane ethoxylate, polysorbates, ethoxylated tristyrylphenol phosphate, sodium lauryl sulphate or sodium methyl oleoyl taurate. Spreading agents is present in the composition in an amount ranging from 0.1 to 10 % w/w.
[0055] The dispersing agent is selected from lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, polystyrenated acrylated co- polymer, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids and mixtures thereof The dispersing agent is present in an amount of from 0.1%
to 15% by weight based on a total weight of the composition.
to 15% by weight based on a total weight of the composition.
[0056] Suitable inert carrier(s) for use in the composition include, but not limited to, natural ground minerals, such as kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, precipitated silica, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz and dolomite, or synthetic granules of inorganic and organic ground materials. The inert carrier is present in an amount of from 1% to 99% by weight based on a total weight of the composition.
[0057] The stabilizing agent is selected from modified hydrophobic silica, colloidal silica, precipitated silica, hydrophobic silica powder and mixtures thereof Preferably, the stabilizing agent is dimethyldichlorosilane-treated fumed silica. In another embodiment, the stabilizing agent is selected from epoxidized soybean oil, gamma butyrolactone, butylated hydroxyl toluene and its derivatives, epichlorhydrin, quinone derivatives, hydrazine hydrates and its derivatives, general class UV stabilizers, glycols and its derivatives and mixtures thereof. The stabilizing agent is present in an amount of from 0 to 6% by weight based on a total weight of the composition.
[0058] The anti-caking agent is selected from kaolin clay, precipitate silica, colloidal silica, fumed silica, talc, gypsum, silicates, calcium carbonate, magnesium carbonate, magnesium sulfate, and mixtures thereof The anti-caking agent is present in an amount of from 0 to 6% by weight based on a total weight of the composition.
[0059] Suitable anti-foaming agents for use in the composition include all substances which normally be used for this purpose in agrochemical compositions. Particularly preferred anti-foaming agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as the silicone anti-foaming agents available from GE or Compton. The anti-foaming agent is present in an amount of from 0 to 2% w/w by weight based on a total weight of the composition.
[0060] Suitable antioxidants are all substances which normally be used for this purpose in agrochemical compositions, as is known in the art. Preferred antioxidant is butylated hydroxytoluene. Antioxidant is present in an amount of from 0 to 5% w/w by weight based on a total weight of the composition.
[0061] Suitable anti-freezing agents include organic solvents which are completely miscible with water, such as ethylene glycol, propylene glycol, other glycols, glycerine or urea. Anti-freezing agent is present in the composition in an amount of from 0 to 5% w/w.
[0062] According to embodiments of the present disclosure, the herbicide composition additionally includes one or more agrochemical active compounds, such as insecticides, nematicides, fungicides, safeners such as cloquintocet methyl or mefenpyr-diethyl, growth factor enhancers or fertilizers, in addition to the components metsulfuron-methyl, clodinafop-propargyl and metribuzin. An agrochemical active compound is present in the composition in an amount ranging from 0 to 6.5% w/w.
[0063] According to embodiments of the present disclosure, the herbicide combination exists as mixed formulations of metsulfuron-methyl, clodinafop-propargyl and metribuzin, which is then be used in a conventional way by diluting with water or prepared as tank mixes by jointly diluting separately formulated or partially separately formulated active ingredients with water or with aqueous solutions.
[0064] In various embodiments, the herbicide composition comprising the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin is formulated in liquid or solid form. In preferred embodiments, the disclosed herbicide composition is formulated as a water-dispersible granule (WDG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), a flowable suspension (FS), a suspoemulsion (SE), ZC formulation (ZC), Soil Applied Granules (SAG), dustable powder (DP), a gel, a water-dispersible tablet (WT), a dispersible concentrate (DC), an oil-dispersion (OD), or a microencapsulated suspension (CS).
[0065] In a preferred embodiment, the herbicide composition comprising the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin is formulated as an oil-dispersion (OD).
[0066] In one embodiment, the herbicide composition comprising the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin is formulated as wettable powder (WP).
[0067] In another embodiment, the herbicide composition comprising the combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin is formulated as water-dispersible granule (WDG).
[0068] The herbicide composition comprising combination of metsulfuron-methyl, clodinafop-propargyl and metribuzin of the present disclosure is useful in controlling growth of undesirable vegetation by post-emergence application. The herbicide composition is applied to undesirable vegetation and/or locus in a variety of ways, at various concentrations. The herbicide composition is applied to the undesirable vegetation and/or locus by various methods, including coating, spraying, sprinkling, dipping, soaking, injection, irrigation, and the like.
[0069] The present disclosure further provides a process for preparing the herbicide composition described herein. The herbicide composition is prepared by mixing the respective active compounds and, if appropriate, one or more inactive excipients.
[0070] The present disclosure is further explained in the form of following examples. However, it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
EXAMPLES
EXAMPLES
[0071] Example 1: Herbicide composition of the present invention.
Table A
Ingredients Concentration (w/w %) Metsulfuron-methyl 0.01 ¨ 10.0 Clodinafop-propargyl 0.1 ¨ 25.0 Metribuzin technical 1.0 ¨ 60.0 Safener 0 ¨ 6.5 Anti crystalline agent 0.1 ¨ 5.0 Emulsifier 1.0¨ 12.0 Wetting agent 0.1 ¨ 8.0 pH modifier 0.01 ¨ 4.0 Rheology modifier 0.1 ¨ 8 Solvent 10-90
Table A
Ingredients Concentration (w/w %) Metsulfuron-methyl 0.01 ¨ 10.0 Clodinafop-propargyl 0.1 ¨ 25.0 Metribuzin technical 1.0 ¨ 60.0 Safener 0 ¨ 6.5 Anti crystalline agent 0.1 ¨ 5.0 Emulsifier 1.0¨ 12.0 Wetting agent 0.1 ¨ 8.0 pH modifier 0.01 ¨ 4.0 Rheology modifier 0.1 ¨ 8 Solvent 10-90
[0072] Oil-dispersion (OD) formulation of the present invention.
Table B
Example-2 Example-3 Example-4 Ingredients Concentration % Concentration Concentration w/w % w/w % w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 vinyl pyrrolidone polymer 2 2 1.5 Ethoxylated ricinoleic acid 5 4 4 triglyceride Dioctyl Sulfosuccinate 5 8 4 Sodium Salt Trisodium Phosphate 0.4 0.5 0.8 Fume silica 4 2.5 3.5 Methyl Soyate QS to 100 QS to 100 QS to 100 (UNITOP ¨ MSO) Total 100 100 100
Table B
Example-2 Example-3 Example-4 Ingredients Concentration % Concentration Concentration w/w % w/w % w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 vinyl pyrrolidone polymer 2 2 1.5 Ethoxylated ricinoleic acid 5 4 4 triglyceride Dioctyl Sulfosuccinate 5 8 4 Sodium Salt Trisodium Phosphate 0.4 0.5 0.8 Fume silica 4 2.5 3.5 Methyl Soyate QS to 100 QS to 100 QS to 100 (UNITOP ¨ MSO) Total 100 100 100
[0073] Oil-dispersion (OD) formulation of the present invention.
Table C
Example-5 Example-6 Example-7 Ingredients Concentration % Concentration Concentration w/w % w/w % w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 Vinyl pyrrolidone polymer 2 2 1.5 Castor oil ethoxylate 5 4 4 (Emulsogen EL 360) Dioctyl Sulfosuccinate 5 8 4 Sodium Salt Trisodium Phosphate 0.4 0.5 0.8 Fume silica 4 2.5 3.5 Rapeseed methyl ester QS to 100 QS to 100 QS to 100 (Agnique ME 18 RD-F) Total 100 100 100
Table C
Example-5 Example-6 Example-7 Ingredients Concentration % Concentration Concentration w/w % w/w % w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 Vinyl pyrrolidone polymer 2 2 1.5 Castor oil ethoxylate 5 4 4 (Emulsogen EL 360) Dioctyl Sulfosuccinate 5 8 4 Sodium Salt Trisodium Phosphate 0.4 0.5 0.8 Fume silica 4 2.5 3.5 Rapeseed methyl ester QS to 100 QS to 100 QS to 100 (Agnique ME 18 RD-F) Total 100 100 100
[0074] The process for preparing the Oil-dispersion (OD) formulation comprises the steps as below:
[0075] Metsulfuron-methyl, clodinafop-propargyl, metribuzin, cloquintocet methyl, vinyl pyrrolidone polymer, ethoxylated ricinoleic acid triglyceride, dioctyl sulfosuccinate sodium salt and trisodium phosphate as mentioned in Examples 2 to 4 were mixed in methyl soyate (UNITOP ¨ MSO) to prepare a mixture. The mixture was milled using Dyno mill for 30 mins to obtain the slurry of desirable particle size, D90 <10 micron. The slurry was mixed in a vessel under PBT stirrer at 300 rpm and fume silica was added as rheology modifier to obtain a homogeneous oil-dispersion (OD).
[0076] Metsulfuron-methyl, clodinafop-propargyl, metribuzin, cloquintocet methyl, vinyl pyrrolidone polymer, castor oil ethoxylate (Emulsogen EL 360), dioctyl sulfosuccinate sodium salt and trisodium phosphate as mentioned in Example 5 to 7 were mixed in rapeseed methyl ester (Agnique ME 18 RD-F) to prepare a mixture. The mixture was milled using Dyno mill for 30 mins to obtain the slurry of desirable particle size, D90 <10 micron. The slurry was mixed in a vessel under PBT stirrer at 300 rpm and fume silica was added as rheology modifier to obtain a homogeneous oil-dispersion (OD).
[0077] According to the FAO/WHO manual, the "accelerated storage test" is considered as an indicative of product stability. That is accelerated storage test data provides an indication that the product is stable for at least two years at ambient temperature. Further, the FAO/WHO manual indicates storage at 54 C 2 C for 14 days as the default test conditions.
[0078] The ambient sample of the oil-dispersion (OD) formulation of the present invention was subjected to the accelerated storage test to find out the product stability.
[0079] Table 1 shows the physical and chemical properties of the oil-dispersion (OD) formulation, before and after the accelerated storage test.
The oil-dispersion (OD) formulation was prepared according to Example 5.
Table 1 Accelerated Test Storage Method Ambient 51. Specification Test Tests Sample No *54 2 C
(before) for 14 days (after) 1. Appearance White to off-white coloured suspension complies complies Visual observation 2 Active Metsulfuron- HPLC
Ingredient/ methyl 0 40 0.39 .
safener content 0.38 ¨ 0.44 (2.5%) content test % Clodinafop- HPLC
5.70 ¨ 6.60 5.98 w/w propargyl 6.0 (0.33%) content Metribuzin 19.95-22.05 21 0 20.89 HPLC
.
content (0.52%) Cloquintocet 1.65 ¨ 1.42 1.5 HPLC
methyl 1.5 (0.0%) content 3. Wet sieve passing through 98 99.94 CIPAC
75 sieve, % w/w, min (particle 99.92 MT
size ) 4.
Dispersion stability CIPAC
Time after Limits of stability MT
allowing the dispersion to stand 0 h Initial dispersion complete 0.5 h Cream, Free oil or Complies Complies sediment max 2m1 in 100m1 dilution 24.0 h Re-dispersion complete 24.5 h Cream, Free oil or sediment max 2m1 in 100m1 dilution 5. pH
(1% aqueous 7.0 ¨ 9.5 CIPAC
773 7.74 suspension) . MT
75.3 6.
Persistent foam after 1 60 CIPAC
min, mL, max MT
47.2 7. Pourability as rinse 1.0 .. 0.3 .. CIPAC
residue, % w/w 0.3 MT 148.1
The oil-dispersion (OD) formulation was prepared according to Example 5.
Table 1 Accelerated Test Storage Method Ambient 51. Specification Test Tests Sample No *54 2 C
(before) for 14 days (after) 1. Appearance White to off-white coloured suspension complies complies Visual observation 2 Active Metsulfuron- HPLC
Ingredient/ methyl 0 40 0.39 .
safener content 0.38 ¨ 0.44 (2.5%) content test % Clodinafop- HPLC
5.70 ¨ 6.60 5.98 w/w propargyl 6.0 (0.33%) content Metribuzin 19.95-22.05 21 0 20.89 HPLC
.
content (0.52%) Cloquintocet 1.65 ¨ 1.42 1.5 HPLC
methyl 1.5 (0.0%) content 3. Wet sieve passing through 98 99.94 CIPAC
75 sieve, % w/w, min (particle 99.92 MT
size ) 4.
Dispersion stability CIPAC
Time after Limits of stability MT
allowing the dispersion to stand 0 h Initial dispersion complete 0.5 h Cream, Free oil or Complies Complies sediment max 2m1 in 100m1 dilution 24.0 h Re-dispersion complete 24.5 h Cream, Free oil or sediment max 2m1 in 100m1 dilution 5. pH
(1% aqueous 7.0 ¨ 9.5 CIPAC
773 7.74 suspension) . MT
75.3 6.
Persistent foam after 1 60 CIPAC
min, mL, max MT
47.2 7. Pourability as rinse 1.0 .. 0.3 .. CIPAC
residue, % w/w 0.3 MT 148.1
[0080] The results in Table 1 show that the appearance of the ambient sample of the oil-dispersion (OD) formulation before and after the accelerated storage test (@54 2 C for 14 days) remained the same that is 'white to off-white coloured suspension'.
[0081] Further, the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be 0.40% w/w, 6.00% w/w, 21.00% w/w, 1.50 % w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54 2 C for 14 days in the HDPE
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be almost same, that is 0.39%w/w, 5.98 %w/w, 20.89%w/w, 1.50 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be almost same, that is 0.39%w/w, 5.98 %w/w, 20.89%w/w, 1.50 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
[0082] The pH of the ambient sample of the OD formulation before subjecting it to the accelerated storage test was found to be 7.73. However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 7.74. It indicates that the oil-dispersion was adhering to the pH range of 7.0 -9.5 which indicates that the formulation is stable.
[0083] Dispersion stability test is performed to ensure that a sufficient proportion of active ingredient is homogeneously dispersed in the spray liquid to give a satisfactory and effective mixture throughout spraying. The ambient sample and accelerated storage sample of the oil-dispersion (OD) formulation, subjected to dispersion stability test did not show any cream or sedimentation even after 0.5 hours of the dispersion or 24.5 hours of the re-dispersion test.
[0084] Tests such as persistent foam and pourability were conducted for the ambient sample of the oil-dispersion (OD) formulation, before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 20 ml and 22 ml indicating the less froth formation and pourability test showed low rinse residue of 0.3%, which indicates no wastage of the formulation.
[0085] The ambient sample of the oil-dispersion (OD) formulation was diluted in water and was tested for its particle size by wet sieve passing test by using 7511 wet sieve. The wet sieve passing test showed passing of 99.94%w/w and 99.92%w/w of particles of the formulation through the 7511 wet sieve indicating the low particle size of the formulation and no crystal growth after the accelerated storage test.
[0086] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[0087] In view of the above test results, oil-dispersion (OD) formulation of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[0088] Example 8: Herbicide composition of the present invention.
Table D
Ingredients Concentration (w/w %) Metsulfuron-methyl 0.01 ¨ 10.0 Clodinafop-propargyl 0.1 ¨ 25.0 Metribuzin 1.0¨ 60.0 Safener 0 ¨ 6.5 Spreading agent 0.1 ¨ 10.0 Dispersing agent 0.1 -15 Wetting agent 0.1 ¨ 8.0 pH modifier 0.01 ¨ 4.0 Inert carrier 1 - 99
Table D
Ingredients Concentration (w/w %) Metsulfuron-methyl 0.01 ¨ 10.0 Clodinafop-propargyl 0.1 ¨ 25.0 Metribuzin 1.0¨ 60.0 Safener 0 ¨ 6.5 Spreading agent 0.1 ¨ 10.0 Dispersing agent 0.1 -15 Wetting agent 0.1 ¨ 8.0 pH modifier 0.01 ¨ 4.0 Inert carrier 1 - 99
[0089] Wettable powder (WP) and Water-dispersible granule (WDG) formulation of the present invention.
Table E
Example-9 Example-10 Example-11 Ingredients Concentration Concentration % Concentration %
% w/w w/w w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 Ethoxylated 4.0 3.5 5 tristyrylphenol phosphate polystyrenated acrylated 10 10 12 co- polymer Sodium alkyl Naphthalene 3 3.5 4.0 Sulfonate Trisodium Phosphate 1 0.7 1.2 Precipitated silica 20 17 23.5 China Clay QS to 100 QS to 100 QS to 100 Total 100 100 100
Table E
Example-9 Example-10 Example-11 Ingredients Concentration Concentration % Concentration %
% w/w w/w w/w Metsulfuron-methyl 0.4 0.5 0.8 Clodinafop-propargyl 6.0 5.0 10 Metribuzin 21.0 32 25 Cloquintocet methyl 1.5 1.4 2.5 Ethoxylated 4.0 3.5 5 tristyrylphenol phosphate polystyrenated acrylated 10 10 12 co- polymer Sodium alkyl Naphthalene 3 3.5 4.0 Sulfonate Trisodium Phosphate 1 0.7 1.2 Precipitated silica 20 17 23.5 China Clay QS to 100 QS to 100 QS to 100 Total 100 100 100
[0090] The process for preparing the Wettable powder (WP) and Water-dispersible granule (WDG) formulation comprises the steps as below.
[0091] A blend of 0.4% w/w metsulfuron-methyl, 21% w/w metribuzin, 10%
w/w polystyrenated acrylated co-polymer, 3% sodium alkyl naphthalene sulfonate, 1% w/w trisodium phosphate and 33.1 % w/w china clay was prepared by blending them for 1 hour. The blend was passed through airjet mill to prepare a milled material having a reduced particle size (D90 <180.
w/w polystyrenated acrylated co-polymer, 3% sodium alkyl naphthalene sulfonate, 1% w/w trisodium phosphate and 33.1 % w/w china clay was prepared by blending them for 1 hour. The blend was passed through airjet mill to prepare a milled material having a reduced particle size (D90 <180.
[0092] 6.0 %w/w clodinafop-propargyl and/or 1.5 w/w cloquintocet methyl was weighed into a clean vessel fitted with pressurised spray gun. The 6.0 %w/w clodinafop-propargyl and/or 1.5 w/w cloquintocet methyl mixture was heated at 60 C-65 C to melt completely. 4.0% w/w ethoxylated tristyrylphenol phosphate was added into it and mixed well to obtain the melted form of clodinafop-propargyl. Melted form of clodinafop-propargyl mixture was uniformly sprayed on 20%w/w precipitated silica by a pressurised spray gun and continued to mix for lhr.
[0093] The melted form of clodinafop-propargyl was charged into the previously prepared milled material and continued to mix for 2 hours to get homogenised wet table powder.
[0094] Water-dispersible granule (WDG) was prepared by charging the previously prepared wet table powder (WP) into the dough maker to prepare uniform dough. The dough was extruded through basket type extruder to get the granules. The granules were dried in a fluidized bed dryer (FBD) at 45 C.
[0095] The ambient sample of the wettable powder (WP) of the present invention was subjected to the accelerated storage test to find out the product stability.
[0096] Table 2 shows the physical and chemical properties of the WP
formulation, before and after the accelerated storage test. The WP formulation was prepared according to Example 9.
Table 2 Accelerate Test d Storage SI. Tests Specification Ambient Method Test Sample No. *54 2 C
for 14 days 1 Appearance White to off white complies complies Visual color powder 2 Active Metsulfuron- 0.40 0.38 HPLC
Ingredie methyl 0.38 ¨ 0.44 (5%) method nt/
safener Clodinafop- 6.0 5.92 content propargyl 5.70 ¨ 6.60 (1.3%) test %
w/w Metribuzin 19.95 ¨ 22.05 21.0 20.93 (0.33%) Cloquintocet 1.65 ¨ 1.42 1.50 1.48 methyl (1.3%) 3 Wet sieve, passing 98 99.5 99.3 CIPAC MT
through 75 sieve, 185 %w/w,Min 4 Suspensibility, , 70 87 82 CIPAC MT
(%w/w),Min 184 Wettability,sec,Max 120 90 81 CIPAC MT
53.3.1 6 pH (1% aq.dispersion) 7.0 ¨ 9.5 7.8 7.7 CIPAC MT
75.3 7 Persistent foam,mL,Max 60 30 32 CIPAC MT
47.2
formulation, before and after the accelerated storage test. The WP formulation was prepared according to Example 9.
Table 2 Accelerate Test d Storage SI. Tests Specification Ambient Method Test Sample No. *54 2 C
for 14 days 1 Appearance White to off white complies complies Visual color powder 2 Active Metsulfuron- 0.40 0.38 HPLC
Ingredie methyl 0.38 ¨ 0.44 (5%) method nt/
safener Clodinafop- 6.0 5.92 content propargyl 5.70 ¨ 6.60 (1.3%) test %
w/w Metribuzin 19.95 ¨ 22.05 21.0 20.93 (0.33%) Cloquintocet 1.65 ¨ 1.42 1.50 1.48 methyl (1.3%) 3 Wet sieve, passing 98 99.5 99.3 CIPAC MT
through 75 sieve, 185 %w/w,Min 4 Suspensibility, , 70 87 82 CIPAC MT
(%w/w),Min 184 Wettability,sec,Max 120 90 81 CIPAC MT
53.3.1 6 pH (1% aq.dispersion) 7.0 ¨ 9.5 7.8 7.7 CIPAC MT
75.3 7 Persistent foam,mL,Max 60 30 32 CIPAC MT
47.2
[0097] The results in Table 2 show that the appearance of the ambient sample of the WP formulation before and after the accelerated storage test (@54 2 C
for 14 days) remained the same that is 'white to off-white coloured powder'.
5 [0098] Further, the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be 0.40% w/w, 6.00 %w/w, 21% w/w, 1.50 %w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54 2 C for 14 days in the HDPE
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is found to be almost same, that is 0.38%
w/w, , 5.92 %w/w, 20.93% w/w, 1.48 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
[0099] The pH of the ambient sample of the wettable powder (WP) before subjecting it to the accelerated storage test was found to be 7.8. However, even after subjecting the ambient sample to the accelerated storage test the pH
was found to be almost same, that is 7.7. It indicates that the wettable powder (WP) was adhering to the pH range of 7.0 ¨ 9.5 which indicates that the formulation is stable.
[00100] The suspensibility test was conducted for the ambient sample of the wettable powder (WP) formulation, before and after accelerated storage test. The results of the suspensibility test indicated that, 87% and 82 % of WP
formulation are uniformly distributed in water after dilution.
[00101] Tests such as persistent foam and wettability were also conducted for the ambient sample of the wettable powder (WP), before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 30m1 and 32m1 indicating the less froth formation. The wettability test showed that the time taken to wet the powder is only 90 and seconds indicating the fast wetting of the powder upon water dilution. The wet sieve passing test showed passing of 99.50%w/w and 99.30%w/w of particles of the formulation through the 7511 wet sieve indicating the low particle size of the formulation.
[00102] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[00103] In view of the above test results, wettable powder (WP) of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[00104] The ambient sample of the water-dispersible granule (WDG) formulation of the present invention is subjected to the accelerated storage test to find out the product stability.
[00105] Table 3 shows the physical and chemical properties of the WDG
formulation, before and after the accelerated storage test. The WDG
formulation is prepared according to Example 9.
Table 3 Accelerated Test Storage Sl. Tests Specification Ambient Method Test Sample No. *54 2 C
for 14 days 1 Appearance White to off complies complies Visual white color granule 2 Active Metsulfuron- 0.40 0.39 HPLC
Ingredient/ methyl 0.38 ¨ 0.44 (2.5%) method safener content Clodinafop- 6.0 5.9 test % Propargyl 5.70 ¨ 6.60 (1.6%) w/w Metribuzin 21.0 20.18 19.95 ¨ 22.05 (3.9%) Cloquintocet 1.65 ¨ 1.42 1.5 1.49 methyl (0.66%) 3 Wet sieve, passing 98 99.6 99.1 CIPAC
through 75[1. sieve, %w/w MT 185 4 Suspensibility, , %w/w 70 82 77 CIPAC
Degree of dispersion, 70 75 71 CIPAC
%w/w MT 174 6 Wettability, sec 120 15 10 CIPAC
MT
53.3.1 7 pH (1% aq.dispersion) 7.0 ¨ 9.5 7.9 7.8 CIPAC
MT
75.3 8 Persistent foam, mL 60 28 30 CIPAC
MT
47.2 9 Moisture content, %, max 5 1.72 1.69 CIPAC
MT
30.1 [00106] The results in Table 3 show that the appearance of the ambient sample of the water-dispersible granule (WDG) before and after the accelerated storage test (@54 2 C for 14 days) remained the same that is 5 'White to off white color granule'.
[00107] Further, the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be 0.40% w/w, 6.00 %w/w, 21.00% w/w, 1.50 %w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54 2 C for 14 days in the HDPE
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be almost same, that is 0.39% w/w , 5.9 %w/w, 20.18% w/w, 1.49 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
[00108] The pH of the ambient sample of the water dispersible granule (WDG) before subjecting it to the accelerated storage test was found to be 7.9.
However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 7.8. It indicates that the water dispersible granule (WDG) was adhering to the pH range of 7.0 ¨ 9.5 which indicates that the formulation is stable.
[00109] The suspensibility test was conducted for the ambient sample of the water dispersible granule (WDG) formulation, before and after accelerated storage test. The results of the suspensibility test indicated that, 82% and 77%
of WP formulation are uniformly distributed in water after dilution.
[00110] Tests such as persistent foam, wettability and degree of dispersion and moisture content were also conducted for the ambient sample of the water dispersible granule (WDG), before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 28m1 and 30m1 indicating the less froth formation. The wettability test showed that the time taken to wet the granules is only 15 and 10 seconds indicating the faster dispersion and disintegration of the granules upon water dilution.
Degree of dispersion test showed that 75% and 71% of granules were dispersed uniformly and formed homogeneous dispersion. Moisture content test showed low moisture content of 1.72% and 1.69% indicating dried granules. The wet sieve passing test showed passing of 99.60%w/w and 99.10%w/w of particles of the formulation through the 7511 wet sieve indicating the low particle size of the formulation.
[00111] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[00112] In view of the above test results, water dispersible granule (WDG) of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[00113] Experimental data:
Table 4: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation against major weeds in wheat variety HD 2967 at the Geong, Kaithal, Kamal and Chandigarh location in the Rabi season 2020.
Table 4 Mean no. of weeds/Sq.mt area Dosage ( 30 days after application) Treatment Broad leaf Formulation g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 180.3 82.7 263.0 Metsulfuron-methyl 20%WP 4 20 181.0 13.5 194.5 Clodinafop- propargyl 60 400 85.3 83.0 168.3 15%WP
Metribuzin 70%WP 210 300 54.5 25.0 79.5 Clodinafop-propargyl 12% +
81+ 283.5 675 45.7 27.5 73.2 Metribuzin 42% WDG
Clodinafop-propargyl 15% +
60+4 400 96.5 29.5 126.0 Metsulfuron-methyl 1% WP
Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 4 + 60 + 210 1000 13.4 8.9 22.3 (recommended Dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
900 20.5 11.3 31.8 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% +
clodinafop-propargyl 6% +3.2 + 48 +
800 26.8 16.3 43.1 Metribuzin 21% OD 168 (20% reduced recommended dosage) [00114] From the above results, after 30 days of application of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% Metribuzin OD formulation, the number of weeds were reduced to a greater extent (22.3 weeds/sq.mt area) that is at least 11 times in comparison to the untreated check (without herbicide treatment) (263.0 weeds/sq.mt area). Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (194.5 weeds/sq.mt area), clodinafop- propargyl 15%WP (168.3 weeds/sq.mt area), metribuzin 70%WP
(79.5 weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (73.2 weeds/Sq.mt area), clodinafop-propargyl 15% + metsulfuron-methyl 1% WP (126.0 weeds/sq.mt area).
[00115] The data of Table 4 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
[00116] Similar result of reduced number of weeds was observed for composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin at 20% reduced recommended dosage of the compounds compared to individual compounds and conventional herbicidal combinations.
Table 5: The results in terms of percent reduction over the untreated check (UTC).
Table 5 % Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
on %Mean g al/ha Grasses (Broad Leaf control (g/ml/ha) Weed) Untreated check Metsulfuron-methyl 83.7(BLW
4 20 0.0 83.7 20%WP only) Clodinafop-propargyl 52.7(Grasses 60 400 52.7 0.0 15%WP only) Metribuzin 70%WP 210 300 69.8 69.8 69.77 Clodinafop-propargyl 12% + Metribuzin 42% 81+ 283.5 675 74.7 66.7 70.70 WDG
Clodinafop-propargyl 15% + Metsulfuron- 60+4 400 46.5 64.3 55.40 methyl 1% WP
Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
4 + 60 + 210 1000 92.6 89.2 90.90 Metribuzin 21% OD
(Recommended Dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
3.6 + 54 +
Metribuzin 21% OD 189 900 88.6 86.3 87.48 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
3.2 + 48 +
Metribuzin 21% OD 168 800 85.1 80.3 82.71 (20% reduced recommended dosage) *BLW-Broad leaved weeds.
[00117] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 90 % reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00118] Table 6: Effect of pre-mix metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% wettable powder (WP) and water-dispersible granule (WDG) formulation against major weeds in wheat at the Chandigarh location in the Rabi season 2020.
Table 6 Mean no. of weeds/Sq.mt area Dosage (30 days after Treatment application) Formulation g a.i./ha Grasses BLW Total (g/ml/ha) Untreated check 144 59 203 Metsulfuron-methyl 20%WP 4 20 144 9 153 Clodinafop-propargyl 15%WP 60 400 78 59 137 Metribuzin 70%WP 210 300 42 17 59 Clodinafop-propargyl 12% +
Metribuzin 42% WDG 81+283.5 675 40 21 61 (2 way combination) Clodinafop-propargyl 15% +60+4 400 82 18 100 Metsulfuron-methyl 1% WP
(2 way combination) Pinoxaden 5.1%EC @ 900m1/ha 900 49 53 102 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 +
Metribuzin 21% WP 210 (Recommended dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 +
Metribuzin 21% WDG 210 1000 33 22 56 (Recommended dosage) [00119] From the above results, after 30 days of application of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% metribuzin WP formulation and WDG formulation, the number of weeds were reduced to a greater extent (43 weeds/sq.mt area and 56 weeds/sq.mt respectively) that is at least 3 to 4 times in comparison to the untreated check (without herbicide treatment) (203 weeds/sq.mt area). Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (153 weeds/sq.mt area), clodinafop-propargyl 15%WP (137 weeds/sq.mt area), Metribuzin 70%WP (59 weeds/sq.mt area) and the conventional herbicide Pinoxaden 5.1%EC (102 weeds/sq.mt area) and conventional two way combinations clodinafop-propargyl 12% +
metribuzin 42% WDG (61 weeds/sq.mt area) and clodinafop-propargyl 15% +
metsulfuron-methyl 1% WP (100weeds/sq.mt area).
Table 7: The result in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulation % Mean g a.i./ha Grasses BLW
(g/ml/ha) control Untreated check 0.0 0.0 0.0 Metsulfuron-methyl 20%WP 4 20 0 85 85(BLW
only) 45(Grasses Clodinafop-propargyl 15%WP 60 400 45 0 only) Metribuzin 70%WP 210 300 70 66 68 Clodinafop-propargyl 12% +
Metribuzin 42% WDG 81+675 68 283.5 (2 way combination) 71 64 Clodinafop-propargyl 15% +
Metsulfuron-methyl 1% WP 60+4 400 57 (2 way combination) 43 72 67(Grasses Pinoxaden 5.1%EC@ 900m1/ha - 900 67 0 only) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% + 4 + 60 +
Metribuzin 21% WP 210 1000 (Recommended dosage) 80 73 77 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% + 4 + 60 +
Metribuzin 21% WDG 210 (Recommended dosage) 75 62 69 [00120] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP and WDG
formulation resulted in higher weeds percent reduction of 77% and 69%
respectively in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
Table 8: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation and wettable powder (WP) formulation against major weeds in wheat variety HD 2967 at the Geong, Kaithal, Karnal and Chandigarh location in the Rabi season 2021.
Table 8 Mean no. of weeds/Sq.mt area Dosage ( 45 days after application) Treatment Broad leaf Formulation g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 260.3 7.7 268.0 Metsulfuron-methyl 20%WP 4 20 260 0.0 260.0 Clodinafop- propargyl 15%WP 125.6 7.5 133.1 Metribuzin 70%WP 210 300 80.7 1.5 82.2 Clodinafop-propargyl 12% +
60+ 210 500 Metribuzin 42% WDG 69 1.2 70.2 Clodinafop-propargyl 9% +
54+120 600 Metribuzin 20% WP 93.6 2.4 96.0 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 4 + 60 + 210 1000 (recommended Dosage) 21.3 0.0 21.3 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
(10% reduced recommended dosage) 24.7 0.0 24.7 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 + 210 1000 Metribuzin 21% WP 59.5 0.0 59.5 (Recommended dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 3.6 + 54 +
(10% reduced recommended dosage) 63.5 0.0 63.5 [00121] From the above results, after 45 days of application of the OD
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (21.3 weeds/sq.mt area) that is at least 12 times in comparison to the untreated check (without herbicide treatment) (268.0weeds/sq.mt area). Also, after 45 days of application of the WP
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (59.5 weeds/sq.mt area) that is at least 4 times in comparison to the untreated check (without herbicide treatment) (268.0weeds/sq.mt area).
[00122] Further, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (260 weeds/sq.mt area), clodinafop-propargyl 15 %WP (133.1 weeds/sq.mt area), metribuzin 70%WP
(82.2weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (70.2 weeds/sq.mt area), clodinafop-propargyl 9% + Metribuzin 20% WP (96 weeds/sq.mt area).
[00123] The data of Table 8 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
Table 9: The results in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
Mean g a.i./ha onGrasses (Broad Leaf control _(g/ml/ha) Weed) Untreated check Metsulfuron-methyl 20%WP 0 100 50 Clodinafop-propargyl 15%WP 51.7 0 25.9 Metribuzin 70%WP 210 300 69 80.5 74.8 Clodinafop-propargyl 60+ 210 500 73.32 84.37 78.8 12% + Metribuzin 42%
WDG
Clodinafop-propargyl 9%
54+120 600 + Metribuzin 20% WP 64 68.3 66.2 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+4 + 60 + 210 1000 Metribuzin 21% OD
(Recommended Dosage) 91.8 100 95.9 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+3.6 + 54 +
Metribuzin 21% OD
(10% reduced recommended dosage) 90.5 100 95.3 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+4 + 60 + 210 1000 Metribuzin 21% WP
(Recommended dosage) 77.14 100 88.55 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% WP 900 (10% reduced recommended dosage) 75.6 100 87.8 *BLW-Broad leaved weeds.
[00124] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 95% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00125] Also, from the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP
formulation resulted in more than 87% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
Table 10: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation and wettable powder (WP) formulation against major weeds in wheat variety HD
2967 at the Geong, Kaithal, Karnal and Chandigarh location in the Rabi season 2021.
Table 10 Mean no. of weeds/Sq.mt area Dosage ( 45 days after application) Treatment Formulation Broad leaf g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 304.67 10.5 315.17 Metsulfuron-methyl 20%WP 4 20 304.33 1 305.33 Clodinafop- propargyl 15%WP 142.00 10 152.00 Metribuzin 70%WP 210 300 90.50 3.0 93.50 Clodinafop-propargyl 12% +
60+ 210 500 Metribuzin 42% WDG 74.83 2.3 77.13 Clodinafop-propargyl 9% +
54+120 600 Metribuzin 20% WP 105.67 4.8 110.47 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 + 210 1000 Metribuzin 21% OD 33.17 0 33.17 (recommended Dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
(10% reduced recommended dosage) 48.67 0 48.67 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 4 + 60 + 210 1000 (Recommended dosage) 50.33 0.5 50.83 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 3.6 + 54 +900 (10% reduced recommended dosage) 57.67 0.5 58.17 [00126] From the above results, after 45 days of application of the OD
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (33.17 weeds/sq.mt area) that is at least 9 times in comparison to the untreated check (without herbicide treatment) (315.17 weeds/sq.mt area). Also, after 45 days of application of the WP
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (50.83 weeds/sq.mt area) that is at least 6 times in comparison to the untreated check (without herbicide treatment) (315.17weeds/sq.mt area).
[00127] Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (305.33 weeds/sq.mt area), clodinafop- propargyl 15%WP (152 weeds/sq.mt area), metribuzin 70%WP
(93.50 weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (77.13 weeds/sq.mt area), clodinafop-propargyl 9% + Metribuzin 20% WP (110.47weed5/sq.mt area).
[00128] The data of Table 10 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
Table 11: The results in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
Mean g a.i./ha onGrasses (Broad Leaf control (g/ml/ha) Weed) Untreated check Metsulfuron-methyl 20%WP
Clodinafop-propargyl 60 400 53.4 0 26.7 15%WP
Metribuzin 70%WP 210 300 70.3 71.42 70.86 Clodinafop-propargyl 12% + Metribuzin 42%60+ 210 500 75.5 78.09 76.8 WDG
Clodinafop-propargyl 9%
54+120 600 65.3 54.28 59.79 + Metribuzin 200/0 WP
Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
4 + 60 + 210 1000 89.1 100 94.55 Metribuzin 21% OD
(Recommended Dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% OD 189 900 84.1 100 92.05 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +4 + 60 + 210 1000 85.59 95.2 90.4 Metribuzin 21% WP
(Recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% WP 189 900 83.53 95.2 89.37 (10% reduced recommended dosage) *BLW-Broad leaved weeds.
[00129] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 92% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00130] Also, from the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP
formulation resulted in more than 89% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
[00131] From the test results shown above, it is evident that there is an unexpected and surprising result, that is synergistic effect of the combination of metsulfuron-methyl, clodinafop-propargyl, metribuzin in the control of weeds such as broad leaved weeds and grassy weeds in wheat fields. As seen from Tables 4 to 11, the combined administration of metsulfuron-methyl, clodinafop-propargyl, and metribuzin resulted in significant reduction in weeds population as compared to single administration of the individual herbicides and the 2 way combination herbicides. As seen from Tables 4 to 11, the present herbicide combination applied in a single treatment to the wheat crop kills substantially all of the weeds, thereby avoiding a need for successive treatments. It is also evident that the combination preparation in accordance with the present invention exhibits a superior herbicidal effect as compared to other known herbicidal products available in the market.
[00132] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed examples will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
for 14 days) remained the same that is 'white to off-white coloured powder'.
5 [0098] Further, the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be 0.40% w/w, 6.00 %w/w, 21% w/w, 1.50 %w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54 2 C for 14 days in the HDPE
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is found to be almost same, that is 0.38%
w/w, , 5.92 %w/w, 20.93% w/w, 1.48 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
[0099] The pH of the ambient sample of the wettable powder (WP) before subjecting it to the accelerated storage test was found to be 7.8. However, even after subjecting the ambient sample to the accelerated storage test the pH
was found to be almost same, that is 7.7. It indicates that the wettable powder (WP) was adhering to the pH range of 7.0 ¨ 9.5 which indicates that the formulation is stable.
[00100] The suspensibility test was conducted for the ambient sample of the wettable powder (WP) formulation, before and after accelerated storage test. The results of the suspensibility test indicated that, 87% and 82 % of WP
formulation are uniformly distributed in water after dilution.
[00101] Tests such as persistent foam and wettability were also conducted for the ambient sample of the wettable powder (WP), before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 30m1 and 32m1 indicating the less froth formation. The wettability test showed that the time taken to wet the powder is only 90 and seconds indicating the fast wetting of the powder upon water dilution. The wet sieve passing test showed passing of 99.50%w/w and 99.30%w/w of particles of the formulation through the 7511 wet sieve indicating the low particle size of the formulation.
[00102] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[00103] In view of the above test results, wettable powder (WP) of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[00104] The ambient sample of the water-dispersible granule (WDG) formulation of the present invention is subjected to the accelerated storage test to find out the product stability.
[00105] Table 3 shows the physical and chemical properties of the WDG
formulation, before and after the accelerated storage test. The WDG
formulation is prepared according to Example 9.
Table 3 Accelerated Test Storage Sl. Tests Specification Ambient Method Test Sample No. *54 2 C
for 14 days 1 Appearance White to off complies complies Visual white color granule 2 Active Metsulfuron- 0.40 0.39 HPLC
Ingredient/ methyl 0.38 ¨ 0.44 (2.5%) method safener content Clodinafop- 6.0 5.9 test % Propargyl 5.70 ¨ 6.60 (1.6%) w/w Metribuzin 21.0 20.18 19.95 ¨ 22.05 (3.9%) Cloquintocet 1.65 ¨ 1.42 1.5 1.49 methyl (0.66%) 3 Wet sieve, passing 98 99.6 99.1 CIPAC
through 75[1. sieve, %w/w MT 185 4 Suspensibility, , %w/w 70 82 77 CIPAC
Degree of dispersion, 70 75 71 CIPAC
%w/w MT 174 6 Wettability, sec 120 15 10 CIPAC
MT
53.3.1 7 pH (1% aq.dispersion) 7.0 ¨ 9.5 7.9 7.8 CIPAC
MT
75.3 8 Persistent foam, mL 60 28 30 CIPAC
MT
47.2 9 Moisture content, %, max 5 1.72 1.69 CIPAC
MT
30.1 [00106] The results in Table 3 show that the appearance of the ambient sample of the water-dispersible granule (WDG) before and after the accelerated storage test (@54 2 C for 14 days) remained the same that is 5 'White to off white color granule'.
[00107] Further, the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be 0.40% w/w, 6.00 %w/w, 21.00% w/w, 1.50 %w/w respectively before subjecting the ambient sample to the accelerated storage test. After subjecting the ambient sample to the accelerated storage test (that is storing at 54 2 C for 14 days in the HDPE
containers) the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl was found to be almost same, that is 0.39% w/w , 5.9 %w/w, 20.18% w/w, 1.49 %w/w respectively. It indicates that the content of metsulfuron-methyl, clodinafop-propargyl, metribuzin and cloquintocet methyl is not degraded.
[00108] The pH of the ambient sample of the water dispersible granule (WDG) before subjecting it to the accelerated storage test was found to be 7.9.
However, even after subjecting the ambient sample to the accelerated storage test the pH was found to be almost same, that is 7.8. It indicates that the water dispersible granule (WDG) was adhering to the pH range of 7.0 ¨ 9.5 which indicates that the formulation is stable.
[00109] The suspensibility test was conducted for the ambient sample of the water dispersible granule (WDG) formulation, before and after accelerated storage test. The results of the suspensibility test indicated that, 82% and 77%
of WP formulation are uniformly distributed in water after dilution.
[00110] Tests such as persistent foam, wettability and degree of dispersion and moisture content were also conducted for the ambient sample of the water dispersible granule (WDG), before and after accelerated storage test. The results indicated that persistent foam test showed low persistent foam of 28m1 and 30m1 indicating the less froth formation. The wettability test showed that the time taken to wet the granules is only 15 and 10 seconds indicating the faster dispersion and disintegration of the granules upon water dilution.
Degree of dispersion test showed that 75% and 71% of granules were dispersed uniformly and formed homogeneous dispersion. Moisture content test showed low moisture content of 1.72% and 1.69% indicating dried granules. The wet sieve passing test showed passing of 99.60%w/w and 99.10%w/w of particles of the formulation through the 7511 wet sieve indicating the low particle size of the formulation.
[00111] Thus, in all the tests, values of the tests remained almost same before and after accelerated storage test which indicates that the formulation is stable.
[00112] In view of the above test results, water dispersible granule (WDG) of the present invention prepared in accordance with the above examples are extrapolated to be stable for 2 years.
[00113] Experimental data:
Table 4: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation against major weeds in wheat variety HD 2967 at the Geong, Kaithal, Kamal and Chandigarh location in the Rabi season 2020.
Table 4 Mean no. of weeds/Sq.mt area Dosage ( 30 days after application) Treatment Broad leaf Formulation g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 180.3 82.7 263.0 Metsulfuron-methyl 20%WP 4 20 181.0 13.5 194.5 Clodinafop- propargyl 60 400 85.3 83.0 168.3 15%WP
Metribuzin 70%WP 210 300 54.5 25.0 79.5 Clodinafop-propargyl 12% +
81+ 283.5 675 45.7 27.5 73.2 Metribuzin 42% WDG
Clodinafop-propargyl 15% +
60+4 400 96.5 29.5 126.0 Metsulfuron-methyl 1% WP
Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 4 + 60 + 210 1000 13.4 8.9 22.3 (recommended Dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
900 20.5 11.3 31.8 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% +
clodinafop-propargyl 6% +3.2 + 48 +
800 26.8 16.3 43.1 Metribuzin 21% OD 168 (20% reduced recommended dosage) [00114] From the above results, after 30 days of application of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% Metribuzin OD formulation, the number of weeds were reduced to a greater extent (22.3 weeds/sq.mt area) that is at least 11 times in comparison to the untreated check (without herbicide treatment) (263.0 weeds/sq.mt area). Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (194.5 weeds/sq.mt area), clodinafop- propargyl 15%WP (168.3 weeds/sq.mt area), metribuzin 70%WP
(79.5 weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (73.2 weeds/Sq.mt area), clodinafop-propargyl 15% + metsulfuron-methyl 1% WP (126.0 weeds/sq.mt area).
[00115] The data of Table 4 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
[00116] Similar result of reduced number of weeds was observed for composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin at 20% reduced recommended dosage of the compounds compared to individual compounds and conventional herbicidal combinations.
Table 5: The results in terms of percent reduction over the untreated check (UTC).
Table 5 % Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
on %Mean g al/ha Grasses (Broad Leaf control (g/ml/ha) Weed) Untreated check Metsulfuron-methyl 83.7(BLW
4 20 0.0 83.7 20%WP only) Clodinafop-propargyl 52.7(Grasses 60 400 52.7 0.0 15%WP only) Metribuzin 70%WP 210 300 69.8 69.8 69.77 Clodinafop-propargyl 12% + Metribuzin 42% 81+ 283.5 675 74.7 66.7 70.70 WDG
Clodinafop-propargyl 15% + Metsulfuron- 60+4 400 46.5 64.3 55.40 methyl 1% WP
Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
4 + 60 + 210 1000 92.6 89.2 90.90 Metribuzin 21% OD
(Recommended Dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
3.6 + 54 +
Metribuzin 21% OD 189 900 88.6 86.3 87.48 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
3.2 + 48 +
Metribuzin 21% OD 168 800 85.1 80.3 82.71 (20% reduced recommended dosage) *BLW-Broad leaved weeds.
[00117] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 90 % reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00118] Table 6: Effect of pre-mix metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% wettable powder (WP) and water-dispersible granule (WDG) formulation against major weeds in wheat at the Chandigarh location in the Rabi season 2020.
Table 6 Mean no. of weeds/Sq.mt area Dosage (30 days after Treatment application) Formulation g a.i./ha Grasses BLW Total (g/ml/ha) Untreated check 144 59 203 Metsulfuron-methyl 20%WP 4 20 144 9 153 Clodinafop-propargyl 15%WP 60 400 78 59 137 Metribuzin 70%WP 210 300 42 17 59 Clodinafop-propargyl 12% +
Metribuzin 42% WDG 81+283.5 675 40 21 61 (2 way combination) Clodinafop-propargyl 15% +60+4 400 82 18 100 Metsulfuron-methyl 1% WP
(2 way combination) Pinoxaden 5.1%EC @ 900m1/ha 900 49 53 102 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 +
Metribuzin 21% WP 210 (Recommended dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 +
Metribuzin 21% WDG 210 1000 33 22 56 (Recommended dosage) [00119] From the above results, after 30 days of application of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% metribuzin WP formulation and WDG formulation, the number of weeds were reduced to a greater extent (43 weeds/sq.mt area and 56 weeds/sq.mt respectively) that is at least 3 to 4 times in comparison to the untreated check (without herbicide treatment) (203 weeds/sq.mt area). Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (153 weeds/sq.mt area), clodinafop-propargyl 15%WP (137 weeds/sq.mt area), Metribuzin 70%WP (59 weeds/sq.mt area) and the conventional herbicide Pinoxaden 5.1%EC (102 weeds/sq.mt area) and conventional two way combinations clodinafop-propargyl 12% +
metribuzin 42% WDG (61 weeds/sq.mt area) and clodinafop-propargyl 15% +
metsulfuron-methyl 1% WP (100weeds/sq.mt area).
Table 7: The result in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulation % Mean g a.i./ha Grasses BLW
(g/ml/ha) control Untreated check 0.0 0.0 0.0 Metsulfuron-methyl 20%WP 4 20 0 85 85(BLW
only) 45(Grasses Clodinafop-propargyl 15%WP 60 400 45 0 only) Metribuzin 70%WP 210 300 70 66 68 Clodinafop-propargyl 12% +
Metribuzin 42% WDG 81+675 68 283.5 (2 way combination) 71 64 Clodinafop-propargyl 15% +
Metsulfuron-methyl 1% WP 60+4 400 57 (2 way combination) 43 72 67(Grasses Pinoxaden 5.1%EC@ 900m1/ha - 900 67 0 only) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% + 4 + 60 +
Metribuzin 21% WP 210 1000 (Recommended dosage) 80 73 77 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% + 4 + 60 +
Metribuzin 21% WDG 210 (Recommended dosage) 75 62 69 [00120] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP and WDG
formulation resulted in higher weeds percent reduction of 77% and 69%
respectively in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
Table 8: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation and wettable powder (WP) formulation against major weeds in wheat variety HD 2967 at the Geong, Kaithal, Karnal and Chandigarh location in the Rabi season 2021.
Table 8 Mean no. of weeds/Sq.mt area Dosage ( 45 days after application) Treatment Broad leaf Formulation g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 260.3 7.7 268.0 Metsulfuron-methyl 20%WP 4 20 260 0.0 260.0 Clodinafop- propargyl 15%WP 125.6 7.5 133.1 Metribuzin 70%WP 210 300 80.7 1.5 82.2 Clodinafop-propargyl 12% +
60+ 210 500 Metribuzin 42% WDG 69 1.2 70.2 Clodinafop-propargyl 9% +
54+120 600 Metribuzin 20% WP 93.6 2.4 96.0 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 4 + 60 + 210 1000 (recommended Dosage) 21.3 0.0 21.3 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
(10% reduced recommended dosage) 24.7 0.0 24.7 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 + 210 1000 Metribuzin 21% WP 59.5 0.0 59.5 (Recommended dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 3.6 + 54 +
(10% reduced recommended dosage) 63.5 0.0 63.5 [00121] From the above results, after 45 days of application of the OD
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (21.3 weeds/sq.mt area) that is at least 12 times in comparison to the untreated check (without herbicide treatment) (268.0weeds/sq.mt area). Also, after 45 days of application of the WP
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (59.5 weeds/sq.mt area) that is at least 4 times in comparison to the untreated check (without herbicide treatment) (268.0weeds/sq.mt area).
[00122] Further, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (260 weeds/sq.mt area), clodinafop-propargyl 15 %WP (133.1 weeds/sq.mt area), metribuzin 70%WP
(82.2weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (70.2 weeds/sq.mt area), clodinafop-propargyl 9% + Metribuzin 20% WP (96 weeds/sq.mt area).
[00123] The data of Table 8 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
Table 9: The results in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
Mean g a.i./ha onGrasses (Broad Leaf control _(g/ml/ha) Weed) Untreated check Metsulfuron-methyl 20%WP 0 100 50 Clodinafop-propargyl 15%WP 51.7 0 25.9 Metribuzin 70%WP 210 300 69 80.5 74.8 Clodinafop-propargyl 60+ 210 500 73.32 84.37 78.8 12% + Metribuzin 42%
WDG
Clodinafop-propargyl 9%
54+120 600 + Metribuzin 20% WP 64 68.3 66.2 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+4 + 60 + 210 1000 Metribuzin 21% OD
(Recommended Dosage) 91.8 100 95.9 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+3.6 + 54 +
Metribuzin 21% OD
(10% reduced recommended dosage) 90.5 100 95.3 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6%
+4 + 60 + 210 1000 Metribuzin 21% WP
(Recommended dosage) 77.14 100 88.55 Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% WP 900 (10% reduced recommended dosage) 75.6 100 87.8 *BLW-Broad leaved weeds.
[00124] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 95% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00125] Also, from the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP
formulation resulted in more than 87% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
Table 10: Effect of pre-mix, metsulfuron-methyl 0.4% + clodinafop-propargyl 6% + metribuzin 21% oil-dispersion (OD) formulation and wettable powder (WP) formulation against major weeds in wheat variety HD
2967 at the Geong, Kaithal, Karnal and Chandigarh location in the Rabi season 2021.
Table 10 Mean no. of weeds/Sq.mt area Dosage ( 45 days after application) Treatment Formulation Broad leaf g a.i./ha Grasses weed Total (g/ml/ha) (BLW) Untreated check 304.67 10.5 315.17 Metsulfuron-methyl 20%WP 4 20 304.33 1 305.33 Clodinafop- propargyl 15%WP 142.00 10 152.00 Metribuzin 70%WP 210 300 90.50 3.0 93.50 Clodinafop-propargyl 12% +
60+ 210 500 Metribuzin 42% WDG 74.83 2.3 77.13 Clodinafop-propargyl 9% +
54+120 600 Metribuzin 20% WP 105.67 4.8 110.47 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +4 + 60 + 210 1000 Metribuzin 21% OD 33.17 0 33.17 (recommended Dosage) Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% OD 3.6 + 54 +
(10% reduced recommended dosage) 48.67 0 48.67 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 4 + 60 + 210 1000 (Recommended dosage) 50.33 0.5 50.83 Metsulfuron-methyl 0.4% +
Clodinafop-propargyl 6% +
Metribuzin 21% WP 3.6 + 54 +900 (10% reduced recommended dosage) 57.67 0.5 58.17 [00126] From the above results, after 45 days of application of the OD
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl, 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (33.17 weeds/sq.mt area) that is at least 9 times in comparison to the untreated check (without herbicide treatment) (315.17 weeds/sq.mt area). Also, after 45 days of application of the WP
formulation of the herbicide composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of 0.4% metsulfuron-methyl , 6% clodinafop-propargyl and 21% metribuzin, the number of weeds were reduced to a greater extent (50.83 weeds/sq.mt area) that is at least 6 times in comparison to the untreated check (without herbicide treatment) (315.17weeds/sq.mt area).
[00127] Also, the results were better in comparison to the individual compounds metsulfuron-methyl 20%WP (305.33 weeds/sq.mt area), clodinafop- propargyl 15%WP (152 weeds/sq.mt area), metribuzin 70%WP
(93.50 weeds/sq.mt area) and the conventional two way combinations of clodinafop-propargyl 12% + metribuzin 42% WDG (77.13 weeds/sq.mt area), clodinafop-propargyl 9% + Metribuzin 20% WP (110.47weed5/sq.mt area).
[00128] The data of Table 10 indicates that the composition having metsulfuron-methyl, clodinafop-propargyl and metribuzin at 10% reduced recommended dosage of the compounds showed higher reduction in the number of weeds than the individual compounds and conventional herbicidal combinations.
Table 11: The results in terms of percent reduction over the untreated check (UTC).
% Control over UTC
Dosage (30 days after application) Treatment Formulati BLW*
Mean g a.i./ha onGrasses (Broad Leaf control (g/ml/ha) Weed) Untreated check Metsulfuron-methyl 20%WP
Clodinafop-propargyl 60 400 53.4 0 26.7 15%WP
Metribuzin 70%WP 210 300 70.3 71.42 70.86 Clodinafop-propargyl 12% + Metribuzin 42%60+ 210 500 75.5 78.09 76.8 WDG
Clodinafop-propargyl 9%
54+120 600 65.3 54.28 59.79 + Metribuzin 200/0 WP
Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +
4 + 60 + 210 1000 89.1 100 94.55 Metribuzin 21% OD
(Recommended Dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% OD 189 900 84.1 100 92.05 (10% reduced recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +4 + 60 + 210 1000 85.59 95.2 90.4 Metribuzin 21% WP
(Recommended dosage) Metsulfuron-methyl 0.4% + Clodinafop-propargyl 6% +3.6 + 54 +
Metribuzin 21% WP 189 900 83.53 95.2 89.37 (10% reduced recommended dosage) *BLW-Broad leaved weeds.
[00129] From the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into OD formulation resulted in more than 92% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the present composition is higher than the individual compounds as well as conventional combinations.
[00130] Also, from the above results, the compositions comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin formulated into WP
formulation resulted in more than 89% reduction of weeds in comparison to the untreated check. The percentage reduction of weeds by the composition is higher than the individual compounds as well as conventional combinations.
[00131] From the test results shown above, it is evident that there is an unexpected and surprising result, that is synergistic effect of the combination of metsulfuron-methyl, clodinafop-propargyl, metribuzin in the control of weeds such as broad leaved weeds and grassy weeds in wheat fields. As seen from Tables 4 to 11, the combined administration of metsulfuron-methyl, clodinafop-propargyl, and metribuzin resulted in significant reduction in weeds population as compared to single administration of the individual herbicides and the 2 way combination herbicides. As seen from Tables 4 to 11, the present herbicide combination applied in a single treatment to the wheat crop kills substantially all of the weeds, thereby avoiding a need for successive treatments. It is also evident that the combination preparation in accordance with the present invention exhibits a superior herbicidal effect as compared to other known herbicidal products available in the market.
[00132] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed examples will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
Claims (23)
1. A herbicide composition comprising a. metsulfuron-methyl;
b. clodinafop-propargyl; and c. metribuzin.
b. clodinafop-propargyl; and c. metribuzin.
2. The herbicide composition as claimed in claim 1, wherein the composition comprises one or more inactive excipients.
3. The herbicide composition as claimed in claim 1 or 2, wherein inactive excipients are selected from the group comprising of one or more of anti-crystalline agent, an emulsifier, a wetting agent, a pH modifier, rheology modifier, a solvent, a spreading agent, a dispersing agent, an inert carrier, a stabilizing agent, an anti-caking agent, an anti-foaming agent, an antioxidant or an anti-freezing agent.
4. The herbicide composition as claimed in claim 1, comprising one or more agrochemical active compounds selected from the group comprising of insecticides, nematicides, fungicides, safeners, growth factor enhancers or fertilizers.
5. The herbicide composition as claimed in claim 1, wherein the composition comprises metsulfuron-methyl in an amount of 0.01% to 10% w/w, clodinafop-propargyl in an amount of 0.1% to 25% w/w, and metribuzin in an amount of 1.0% to 60% w/w.
6. The herbicide composition as claimed in claim 1, wherein the composition comprising metsulfuron-methyl, clodinafop-propargyl and metribuzin in an amount of from 0.1% to 95% by weight of the composition.
7. The herbicide composition as claimed in claim 1, wherein the composition is formulated as a water-dispersible granule (WDG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), a flowable suspension (FS), a suspoemulsion (SE), ZC formulation (ZC), Soil Applied Granules (SAG), dustable powder (DP), a gel, a water-dispersible tablet (WT), a dispersible concentrate (DC), an oil-dispersion (OD) or a microencapsulated suspension (CS).
8. The herbicide composition as claimed in claim 1 or 7, wherein the composition is in the form of an oil-dispersion (OD).
9. The herbicide composition as claimed in claim 8, wherein the oil-dispersion (OD) comprises:
a. metsulfuron-methyl;
b. clodinafop-propargyl;
c. metribuzin;
d. a safener;
e. an anti-crystalline agent;
f. an emulsifier;
g. a wetting agent;
h. a pH modifier;
i. a rheology modifier; and j . an oil medium.
a. metsulfuron-methyl;
b. clodinafop-propargyl;
c. metribuzin;
d. a safener;
e. an anti-crystalline agent;
f. an emulsifier;
g. a wetting agent;
h. a pH modifier;
i. a rheology modifier; and j . an oil medium.
10. The herbicide composition as claimed in claim 9, wherein the oil-dispersion (OD) comprises:
a) 0.01-10% w/w metsulfuron-methyl;
= 30 b) 0.1 ¨ 25% w/w clodinafop-propargyl c) 1.0 ¨ 60.0 % w/w metribuzin;
d) 0 ¨ 6.5 % w/w a safener;
e) 0.1 ¨ 5.0 % w/w an anti-crystalline agent;
f) 1.0 ¨ 12.0% w/w an emulsifier;
g) 0.1 ¨ 8.0 % w/w a wetting agent;
h) 0.01 ¨ 4.0% w/w a pH modifier;
i) 0.1 ¨ 8 %w/w a rheology modifier; and j) 10- 90 %w/w an oil medium.
a) 0.01-10% w/w metsulfuron-methyl;
= 30 b) 0.1 ¨ 25% w/w clodinafop-propargyl c) 1.0 ¨ 60.0 % w/w metribuzin;
d) 0 ¨ 6.5 % w/w a safener;
e) 0.1 ¨ 5.0 % w/w an anti-crystalline agent;
f) 1.0 ¨ 12.0% w/w an emulsifier;
g) 0.1 ¨ 8.0 % w/w a wetting agent;
h) 0.01 ¨ 4.0% w/w a pH modifier;
i) 0.1 ¨ 8 %w/w a rheology modifier; and j) 10- 90 %w/w an oil medium.
11. The herbicide composition as claimed in claim 10, wherein the oil-dispersion (OD) comprises:
a. 0.01-10% w/w of metsulfuron-methyl;
b. 0.1 ¨ 25% w/w of clodinafop-propargyl;
c. 1.0 ¨ 60.0 % w/w of metribuzin;
d. 0 ¨ 6.5 w/w of a safener selected from the group comprising of cloquintocet methyl or mefenpyr-diethyl;
e. 0.1 ¨ 5.0 w/w of an anti-crystalline agent selected from the group comprising of vinyl pyrrolidone polymer, calcium salts of (linear and branched) alkyl benzene sulfonic acid or sodium salt of lignosulfonate;
f. 1.0 ¨ 12.0% w/w of an emulsifier selected from the group comprising of ethoxylated ricinoleic acid triglycerides, tristyryphenol ethoxylate or ethoxylated propoxylated polyarylphenol;
g. 0.1 ¨ 8.0 % w/w of a wetting agent selected from the group comprising of dioctyl sulfosuccinate sodium salt, diisodecyl sodium sulfosuccinate, disodium laureth sulfosuccinate, alpha olefin sulfonates, sodium alkyl naphthalene sulfonate, octyl phenol ether sulphate or anionic phosphate esters;
h. 0.01 ¨ 4.0% w/w of a pH modifier selected from the group comprising of sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate ;
i. 0.1 ¨ 8 %w/w of a rheology modifier selected from the group comprising of hydrophobic silica, fume silica, bentonite, diatomaceous earth, montmorillonite, attapulgites or hydroxymethyl cellulose; and j. 10- 90 %w/w of an oil medium selected from the group comprising, esterified fatty acids selected from methyl ester of triglycerides containing C12 ¨C22 saturated and unsaturated fatty acids, ethyl ester of triglycerides containing C12 ¨C22 saturated and unsaturated fatty acids, bio-diesels, paraffinic oil or tall oil.
a. 0.01-10% w/w of metsulfuron-methyl;
b. 0.1 ¨ 25% w/w of clodinafop-propargyl;
c. 1.0 ¨ 60.0 % w/w of metribuzin;
d. 0 ¨ 6.5 w/w of a safener selected from the group comprising of cloquintocet methyl or mefenpyr-diethyl;
e. 0.1 ¨ 5.0 w/w of an anti-crystalline agent selected from the group comprising of vinyl pyrrolidone polymer, calcium salts of (linear and branched) alkyl benzene sulfonic acid or sodium salt of lignosulfonate;
f. 1.0 ¨ 12.0% w/w of an emulsifier selected from the group comprising of ethoxylated ricinoleic acid triglycerides, tristyryphenol ethoxylate or ethoxylated propoxylated polyarylphenol;
g. 0.1 ¨ 8.0 % w/w of a wetting agent selected from the group comprising of dioctyl sulfosuccinate sodium salt, diisodecyl sodium sulfosuccinate, disodium laureth sulfosuccinate, alpha olefin sulfonates, sodium alkyl naphthalene sulfonate, octyl phenol ether sulphate or anionic phosphate esters;
h. 0.01 ¨ 4.0% w/w of a pH modifier selected from the group comprising of sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate ;
i. 0.1 ¨ 8 %w/w of a rheology modifier selected from the group comprising of hydrophobic silica, fume silica, bentonite, diatomaceous earth, montmorillonite, attapulgites or hydroxymethyl cellulose; and j. 10- 90 %w/w of an oil medium selected from the group comprising, esterified fatty acids selected from methyl ester of triglycerides containing C12 ¨C22 saturated and unsaturated fatty acids, ethyl ester of triglycerides containing C12 ¨C22 saturated and unsaturated fatty acids, bio-diesels, paraffinic oil or tall oil.
12. The herbicide composition as claimed in claim 1 or 7, wherein the composition is in the form of wettable powder (WP).
13. The herbicide composition as claimed in claim 1 or 7, wherein the composition is in the form of water-dispersible granule (WDG).
14. The herbicide composition as claimed in claim 12 or 13, wherein the wettable powder (WP) or water-dispersible granule (WDG) comprises:
a. metsulfuron-methyl;
= 25 b. clodinafop-propargyl c. metribuzin;
d. a safener;
e. a spreading agent;
f. a dispersing agent g. a wetting agent;
h. a pH modifier; and i. an inert carrier.
a. metsulfuron-methyl;
= 25 b. clodinafop-propargyl c. metribuzin;
d. a safener;
e. a spreading agent;
f. a dispersing agent g. a wetting agent;
h. a pH modifier; and i. an inert carrier.
15. The herbicide composition as claimed in claim 14, wherein the wettable powder (WP) or water-dispersible granule (WDG) comprises:
a) 0.01-10% w/w metsulfuron-methyl;
= b) 0.1 ¨ 25% w/w clodinafop-propargyl c) 1.0 ¨ 60.0 % w/w metribuzin;
d) 0 ¨ 6.5 % w/w a safener;
e) 0.1 ¨ 10.0 % w/w a spreading agent;
f) 0.1 ¨ 15 % w/w a dispersing agent g) 0.1 ¨ 8.0 % w/w a wetting agent;
h) 0.01 ¨ 4.0% w/w a pH modifier; and i) 1 ¨ 99 % w/w an inert carrier.
a) 0.01-10% w/w metsulfuron-methyl;
= b) 0.1 ¨ 25% w/w clodinafop-propargyl c) 1.0 ¨ 60.0 % w/w metribuzin;
d) 0 ¨ 6.5 % w/w a safener;
e) 0.1 ¨ 10.0 % w/w a spreading agent;
f) 0.1 ¨ 15 % w/w a dispersing agent g) 0.1 ¨ 8.0 % w/w a wetting agent;
h) 0.01 ¨ 4.0% w/w a pH modifier; and i) 1 ¨ 99 % w/w an inert carrier.
16. The herbicide composition as claimed in claim 15, wherein the wettable powder (WP) or water-dispersible granule (WDG) comprises:
a. 0.01-10% w/w of metsulfuron-methyl;
b. 0.1 ¨ 25% w/w of clodinafop-propargyl;
c. 1.0 ¨ 60.0 % w/w of metribuzin;
d. 0 ¨ 6.5 w/w of a safener selected from the group comprising of cloquintocet methyl or mefenpyr-diethyl;
e. 0.1 ¨ 10.0 % w/w of a spreading agent selected from the group comprising of polyoxyethylene alkyl ether, trisiloxane ethoxylate, polysorbates, ethoxylated tristyrylphenol phosphate, sodium lauryl sulphate or sodium methyl oleoyl taurate.
f. 0.1 ¨ 15 % w/w of a dispersing agent selected from the group comprising of lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, polystyrenated acrylated co- polymer, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids and mixtures thereof g. 0.1 ¨ 8.0 % w/w of a wetting agent selected from the group comprising of dioctyl sulfosuccinate sodium salt, di isodecyl sodium sulfosuccinate, disodium laureth sulfosuccinate, alpha olefin sulfonates, sodium alkyl naphthalene sulfonate, octyl phenol ether sulphate, anionic phosphate esters;
h. 0.01 ¨ 4.0% w/w of a pH modifier selected from the group comprising of sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate; and i. 1 ¨ 99 % w/w of an inert carrier selected from the group comprising of natural ground minerals, such as kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, precipitated silica, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz and dolomite or synthetic granules of inorganic and organic ground materials.
a. 0.01-10% w/w of metsulfuron-methyl;
b. 0.1 ¨ 25% w/w of clodinafop-propargyl;
c. 1.0 ¨ 60.0 % w/w of metribuzin;
d. 0 ¨ 6.5 w/w of a safener selected from the group comprising of cloquintocet methyl or mefenpyr-diethyl;
e. 0.1 ¨ 10.0 % w/w of a spreading agent selected from the group comprising of polyoxyethylene alkyl ether, trisiloxane ethoxylate, polysorbates, ethoxylated tristyrylphenol phosphate, sodium lauryl sulphate or sodium methyl oleoyl taurate.
f. 0.1 ¨ 15 % w/w of a dispersing agent selected from the group comprising of lignosulphonates, phenyl naphthalene sulphonates, ethoxylated alkyl phenols, ethoxylated fatty acids, alkoxylated linear alcohols, polyaromatic sulfonates, sodium alkyl aryl sulfonates, maleic anhydride copolymers, phosphate esters, condensation products of aryl/alkyl sulphonic acids and formaldehyde, addition products of ethylene oxide and fatty acid esters, sulfonates of condensed naphthalene, lignin derivatives, naphthalene formaldehyde condensates, polycarboxylates, sodium alkyl benzene sulfonates, salts of sulfonated naphthalene, polystyrenated acrylated co- polymer, ammonium salts of sulfonated naphthalene, salts of polyacrylic acids, salts of phenol sulfonic acids and mixtures thereof g. 0.1 ¨ 8.0 % w/w of a wetting agent selected from the group comprising of dioctyl sulfosuccinate sodium salt, di isodecyl sodium sulfosuccinate, disodium laureth sulfosuccinate, alpha olefin sulfonates, sodium alkyl naphthalene sulfonate, octyl phenol ether sulphate, anionic phosphate esters;
h. 0.01 ¨ 4.0% w/w of a pH modifier selected from the group comprising of sodium silicate, potassium silicate, magnesium silicate, manganese silicate, sodium pyrophosphate, sodium acetate, sodium oxalate, sodium carbonate, sodium bicarbonate, sodium bentonite, sodium acetate, attapulgite, diatomaceous earth, sodium zeolite, trisodium phosphate, trisodium citrate, magnesium carbonate, magnesium sulphate, monoethanol amine, triethanol amine, triethylamine, dibasic esters selected from dimethyl succinate, dimethyl glutarate or dimethyl adipate; and i. 1 ¨ 99 % w/w of an inert carrier selected from the group comprising of natural ground minerals, such as kaolin or china clay, alumina, talc, chalk, quartz, attapulgite, montmorillonite, and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminium oxide, silicates, and calcium phosphates and calcium hydrogen phosphates, crushed and fractionated natural minerals, such as calcite, marble, pumice, precipitated silica, sepiolite, bentonite, river sand, zeolites, starch, sand, talc, quartz and dolomite or synthetic granules of inorganic and organic ground materials.
17. A process for preparing the composition as claimed in claim 1, the process comprising mixing metsulfuron-methyl, clodinafop-propargyl and metribuzin.
18. The process for preparing the composition as claimed in claim 17 comprising adding one or more inactive excipients in the presence or absence of agrochemical active compounds selected from the group comprising of insecticides, nematicides, fungicides, safeners, growth factor enhancers or fertilizers.
19. The process for preparing the composition as claimed in claim 18, wherein inactive excipients are selected from the group comprising of one or more of anti-crystalline agent, an emulsifier, a wetting agent, a pH modifier, rheology modifier, a solvent, a spreading agent, a dispersing agent, an inert carrier, a stabilizing agent, an anti-caking agent, an anti-foaming agent, an antioxidant or an anti-freezing agent.
20. The process for preparing the composition as claimed in claim 17 or 18, wherein the composition is formulated as a water-dispersible granule (WDG), a water-soluble granule (SG), a wettable powder (WP), a water-dispersible powder (WDP), a water-soluble powder (SP), a granule (GR), an encapsulated granule (CG), a fine granule (FG), a macrogranule (GG), a microgranule (MG), a suspension concentrate (SC), a water-soluble concentrate (SL), an emulsifiable concentrate (EC), an emulsion (EW), a micro-emulsion (ME), a flowable suspension (FS), a suspoemulsion (SE), ZC formulation (ZC), soil applied granules (SAG), dustable powder (DP), a gel, a water-dispersible tablet (WT), a dispersible concentrate (DC), an oil-dispersion (OD) or a microencapsulated suspension (CS).
21. The process as claimed in claim 17 or 20, the process comprising:
a) mixing metsulfuron-methyl, clodinafop-propargyl, metribuzin or safener and one or more excipients to obtain a mixture;
b) milling the mixture to obtain a slurry; and c) stirring the slurry by adding a rheology modifier to obtain a homogeneous oil-dispersion.
a) mixing metsulfuron-methyl, clodinafop-propargyl, metribuzin or safener and one or more excipients to obtain a mixture;
b) milling the mixture to obtain a slurry; and c) stirring the slurry by adding a rheology modifier to obtain a homogeneous oil-dispersion.
22. The process as claimed in claim 17 or 20, the process comprising :
a) preparing a blend of metribuzin, metsulfuron-methyl and one or more inactive excipients;
b) milling the blend of metribuzin, metsulfuron-methyl and one or more inactive excipients for particle size reduction;
c) preparing a melted form of clodinafop-propargyl by mixing with one or more inactive excipients; and d) charging the melted form of clodinafop-propargyl into the milled material with mixing to get homogenised wettable powder (WP).
a) preparing a blend of metribuzin, metsulfuron-methyl and one or more inactive excipients;
b) milling the blend of metribuzin, metsulfuron-methyl and one or more inactive excipients for particle size reduction;
c) preparing a melted form of clodinafop-propargyl by mixing with one or more inactive excipients; and d) charging the melted form of clodinafop-propargyl into the milled material with mixing to get homogenised wettable powder (WP).
23. The process as claimed in claim 17 or 20, the process comprising:
a) preparing a dough from the wettable powder (WP) obtained by the process as claimed in claim 22;
b) extruding the dough to obtain granules; and c) drying the granules to obtain water dispersible granules (WDG).
a) preparing a dough from the wettable powder (WP) obtained by the process as claimed in claim 22;
b) extruding the dough to obtain granules; and c) drying the granules to obtain water dispersible granules (WDG).
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