IT201900006358A1 - Sospensioni non acquose per il controllo della deriva - Google Patents
Sospensioni non acquose per il controllo della deriva Download PDFInfo
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- IT201900006358A1 IT201900006358A1 IT102019000006358A IT201900006358A IT201900006358A1 IT 201900006358 A1 IT201900006358 A1 IT 201900006358A1 IT 102019000006358 A IT102019000006358 A IT 102019000006358A IT 201900006358 A IT201900006358 A IT 201900006358A IT 201900006358 A1 IT201900006358 A1 IT 201900006358A1
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- aqueous suspension
- water
- glycol
- vehicle
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- 239000007900 aqueous suspension Substances 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims description 73
- -1 glycol ethers Chemical class 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 32
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- 239000005017 polysaccharide Substances 0.000 claims description 30
- 229920003169 water-soluble polymer Polymers 0.000 claims description 24
- 238000009472 formulation Methods 0.000 claims description 21
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- 150000002148 esters Chemical class 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920000151 polyglycol Polymers 0.000 claims description 12
- 239000010695 polyglycol Substances 0.000 claims description 12
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002253 acid Substances 0.000 claims description 5
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- 150000004676 glycans Chemical class 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims 2
- 150000003893 lactate salts Chemical class 0.000 claims 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 1
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 6
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 6
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- 125000002091 cationic group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 3
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- 229920002000 Xyloglucan Polymers 0.000 description 3
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- IANUJLZYFUDJIH-UHFFFAOYSA-N flufenacet Chemical compound C=1C=C(F)C=CC=1N(C(C)C)C(=O)COC1=NN=C(C(F)(F)F)S1 IANUJLZYFUDJIH-UHFFFAOYSA-N 0.000 description 3
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- 239000002736 nonionic surfactant Substances 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- ROGDGDPDLIVQFZ-OGFXRTJISA-N (2r)-2-(4-chloro-2-methylphenoxy)propanoic acid;n-methylmethanamine Chemical compound CNC.OC(=O)[C@@H](C)OC1=CC=C(Cl)C=C1C ROGDGDPDLIVQFZ-OGFXRTJISA-N 0.000 description 2
- ROBSGBGTWRRYSK-SNVBAGLBSA-N (2r)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CC=C(C#N)C=C1F ROBSGBGTWRRYSK-SNVBAGLBSA-N 0.000 description 2
- NYHLMHAKWBUZDY-QMMMGPOBSA-N (2s)-2-[2-chloro-5-[2-chloro-4-(trifluoromethyl)phenoxy]benzoyl]oxypropanoic acid Chemical compound C1=C(Cl)C(C(=O)O[C@@H](C)C(O)=O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NYHLMHAKWBUZDY-QMMMGPOBSA-N 0.000 description 2
- WVQBLGZPHOPPFO-LBPRGKRZSA-N (S)-metolachlor Chemical compound CCC1=CC=CC(C)=C1N([C@@H](C)COC)C(=O)CCl WVQBLGZPHOPPFO-LBPRGKRZSA-N 0.000 description 2
- BXKKQFGRMSOANI-UHFFFAOYSA-N 1-methoxy-3-[4-[(2-methoxy-2,4,4-trimethyl-3h-chromen-7-yl)oxy]phenyl]-1-methylurea Chemical compound C1=CC(NC(=O)N(C)OC)=CC=C1OC1=CC=C2C(C)(C)CC(C)(OC)OC2=C1 BXKKQFGRMSOANI-UHFFFAOYSA-N 0.000 description 2
- QOPBEBWGSGFROG-UHFFFAOYSA-N 2-(1h-indol-2-yl)acetic acid Chemical compound C1=CC=C2NC(CC(=O)O)=CC2=C1 QOPBEBWGSGFROG-UHFFFAOYSA-N 0.000 description 2
- KFEFNHNXZQYTEW-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-4-methylbenzoic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=CC(C)=CC=C1C(O)=O KFEFNHNXZQYTEW-UHFFFAOYSA-N 0.000 description 2
- YUVKUEAFAVKILW-UHFFFAOYSA-N 2-(4-{[5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 YUVKUEAFAVKILW-UHFFFAOYSA-N 0.000 description 2
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 description 2
- LLWADFLAOKUBDR-UHFFFAOYSA-N 2-methyl-4-chlorophenoxybutyric acid Chemical compound CC1=CC(Cl)=CC=C1OCCCC(O)=O LLWADFLAOKUBDR-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ABOOPXYCKNFDNJ-UHFFFAOYSA-N 2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 ABOOPXYCKNFDNJ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005575 MCPB Substances 0.000 description 2
- 101150039283 MCPB gene Proteins 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
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- WLFDQEVORAMCIM-UHFFFAOYSA-N Metobromuron Chemical compound CON(C)C(=O)NC1=CC=C(Br)C=C1 WLFDQEVORAMCIM-UHFFFAOYSA-N 0.000 description 2
- 239000005582 Metosulam Substances 0.000 description 2
- VGHPMIFEKOFHHQ-UHFFFAOYSA-N Metosulam Chemical compound N1=C2N=C(OC)C=C(OC)N2N=C1S(=O)(=O)NC1=C(Cl)C=CC(C)=C1Cl VGHPMIFEKOFHHQ-UHFFFAOYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000005617 S-Metolachlor Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- PNRAZZZISDRWMV-UHFFFAOYSA-N Terbucarb Chemical compound CNC(=O)OC1=C(C(C)(C)C)C=C(C)C=C1C(C)(C)C PNRAZZZISDRWMV-UHFFFAOYSA-N 0.000 description 2
- 239000005626 Tribenuron Substances 0.000 description 2
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- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- SILSDTWXNBZOGF-JWGBMQLESA-N clethodim Chemical compound CCSC(C)CC1CC(O)=C(C(CC)=NOC\C=C\Cl)C(=O)C1 SILSDTWXNBZOGF-JWGBMQLESA-N 0.000 description 2
- YIANBKOBVRMNPR-UHFFFAOYSA-N cloransulam Chemical compound N=1N2C(OCC)=NC(F)=CC2=NC=1S(=O)(=O)NC1=C(Cl)C=CC=C1C(O)=O YIANBKOBVRMNPR-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- GINFBXXYGUODAT-UHFFFAOYSA-N flucarbazone Chemical compound O=C1N(C)C(OC)=NN1C(=O)NS(=O)(=O)C1=CC=CC=C1OC(F)(F)F GINFBXXYGUODAT-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- RUCAXVJJQQJZGU-UHFFFAOYSA-M hydron;2-(phosphonatomethylamino)acetate;trimethylsulfanium Chemical compound C[S+](C)C.OP(O)(=O)CNCC([O-])=O RUCAXVJJQQJZGU-UHFFFAOYSA-M 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 2
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- NDNKHWUXXOFHTD-UHFFFAOYSA-N metizoline Chemical compound CC=1SC2=CC=CC=C2C=1CC1=NCCN1 NDNKHWUXXOFHTD-UHFFFAOYSA-N 0.000 description 2
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- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 2
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YXIIPOGUBVYZIW-UHFFFAOYSA-N pyraflufen Chemical compound ClC1=C(OC(F)F)N(C)N=C1C1=CC(OCC(O)=O)=C(Cl)C=C1F YXIIPOGUBVYZIW-UHFFFAOYSA-N 0.000 description 2
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- CHIFOSRWCNZCFN-UHFFFAOYSA-N pendimethalin Chemical compound CCC(CC)NC1=C([N+]([O-])=O)C=C(C)C(C)=C1[N+]([O-])=O CHIFOSRWCNZCFN-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JZPKLLLUDLHCEL-UHFFFAOYSA-N pentoxazone Chemical compound O=C1C(=C(C)C)OC(=O)N1C1=CC(OC2CCCC2)=C(Cl)C=C1F JZPKLLLUDLHCEL-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- CSWIKHNSBZVWNQ-UHFFFAOYSA-N pethoxamide Chemical compound CCOCCN(C(=O)CCl)C(=C(C)C)C1=CC=CC=C1 CSWIKHNSBZVWNQ-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OFCQYQOZASISIU-OGFXRTJISA-M potassium;(2r)-2-(4-chloro-2-methylphenoxy)propanoate Chemical compound [K+].[O-]C(=O)[C@@H](C)OC1=CC=C(Cl)C=C1C OFCQYQOZASISIU-OGFXRTJISA-M 0.000 description 1
- LIOPHZNMBKHGAV-UHFFFAOYSA-M potassium;2-(phosphonomethylamino)acetate Chemical compound [K+].OC(=O)CNCP(O)([O-])=O LIOPHZNMBKHGAV-UHFFFAOYSA-M 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- WHHIPMZEDGBUCC-UHFFFAOYSA-N probenazole Chemical compound C1=CC=C2C(OCC=C)=NS(=O)(=O)C2=C1 WHHIPMZEDGBUCC-UHFFFAOYSA-N 0.000 description 1
- BUCOQPHDYUOJSI-UHFFFAOYSA-N prohexadione Chemical compound CCC(=O)C1C(=O)CC(C(O)=O)CC1=O BUCOQPHDYUOJSI-UHFFFAOYSA-N 0.000 description 1
- ISEUFVQQFVOBCY-UHFFFAOYSA-N prometon Chemical compound COC1=NC(NC(C)C)=NC(NC(C)C)=N1 ISEUFVQQFVOBCY-UHFFFAOYSA-N 0.000 description 1
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- MFOUDYKPLGXPGO-UHFFFAOYSA-N propachlor Chemical compound ClCC(=O)N(C(C)C)C1=CC=CC=C1 MFOUDYKPLGXPGO-UHFFFAOYSA-N 0.000 description 1
- WHOKDONDRZNCBC-UHFFFAOYSA-N propan-2-yl 2-(2,4-dichlorophenoxy)acetate Chemical group CC(C)OC(=O)COC1=CC=C(Cl)C=C1Cl WHOKDONDRZNCBC-UHFFFAOYSA-N 0.000 description 1
- OYJMHAFVOZPIOY-UHFFFAOYSA-N propan-2-yl 2-chloro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoate Chemical compound C1=C(Cl)C(C(=O)OC(C)C)=CC(N2C(N(C)C(=CC2=O)C(F)(F)F)=O)=C1 OYJMHAFVOZPIOY-UHFFFAOYSA-N 0.000 description 1
- REJMLNWDJIPPSE-UHFFFAOYSA-N propan-2-yl 4-[[2-(4,6-dimethoxypyrimidin-2-yl)oxyphenyl]methylamino]benzoate Chemical group COC1=CC(OC)=NC(OC=2C(=CC=CC=2)CNC=2C=CC(=CC=2)C(=O)OC(C)C)=N1 REJMLNWDJIPPSE-UHFFFAOYSA-N 0.000 description 1
- FKLQIONHGSFYJY-UHFFFAOYSA-N propan-2-yl 5-[4-bromo-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-chloro-4-fluorobenzoate Chemical compound C1=C(Cl)C(C(=O)OC(C)C)=CC(C=2C(=C(N(C)N=2)C(F)(F)F)Br)=C1F FKLQIONHGSFYJY-UHFFFAOYSA-N 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PHNUZKMIPFFYSO-UHFFFAOYSA-N propyzamide Chemical compound C#CC(C)(C)NC(=O)C1=CC(Cl)=CC(Cl)=C1 PHNUZKMIPFFYSO-UHFFFAOYSA-N 0.000 description 1
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- DWSPRBSLSXQIEJ-UHFFFAOYSA-N pyrasulfotole Chemical compound CC1=NN(C)C(O)=C1C(=O)C1=CC=C(C(F)(F)F)C=C1S(C)(=O)=O DWSPRBSLSXQIEJ-UHFFFAOYSA-N 0.000 description 1
- FKERUJTUOYLBKB-UHFFFAOYSA-N pyrazoxyfen Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OCC(=O)C1=CC=CC=C1 FKERUJTUOYLBKB-UHFFFAOYSA-N 0.000 description 1
- VTRWMTJQBQJKQH-UHFFFAOYSA-N pyributicarb Chemical compound COC1=CC=CC(N(C)C(=S)OC=2C=C(C=CC=2)C(C)(C)C)=N1 VTRWMTJQBQJKQH-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- FFSSWMQPCJRCRV-UHFFFAOYSA-N quinclorac Chemical compound ClC1=CN=C2C(C(=O)O)=C(Cl)C=CC2=C1 FFSSWMQPCJRCRV-UHFFFAOYSA-N 0.000 description 1
- ALZOLUNSQWINIR-UHFFFAOYSA-N quinmerac Chemical compound OC(=O)C1=C(Cl)C=CC2=CC(C)=CN=C21 ALZOLUNSQWINIR-UHFFFAOYSA-N 0.000 description 1
- ABOOPXYCKNFDNJ-SNVBAGLBSA-N quizalofop-P Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 ABOOPXYCKNFDNJ-SNVBAGLBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MEFOUWRMVYJCQC-UHFFFAOYSA-N rimsulfuron Chemical compound CCS(=O)(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 MEFOUWRMVYJCQC-UHFFFAOYSA-N 0.000 description 1
- GNHDVXLWBQYPJE-UHFFFAOYSA-N saflufenacil Chemical compound C1=C(Cl)C(C(=O)NS(=O)(=O)N(C)C(C)C)=CC(N2C(N(C)C(=CC2=O)C(F)(F)F)=O)=C1F GNHDVXLWBQYPJE-UHFFFAOYSA-N 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 1
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 description 1
- DEWVPZYHFVYXMZ-QCILGFJPSA-M sodium;(3ar,4as,8ar,8bs)-2,2,7,7-tetramethyl-4a,5,8a,8b-tetrahydro-[1,3]dioxolo[3,4]furo[1,3-d][1,3]dioxine-3a-carboxylate Chemical compound [Na+].O([C@H]12)C(C)(C)OC[C@@H]1O[C@]1(C([O-])=O)[C@H]2OC(C)(C)O1 DEWVPZYHFVYXMZ-QCILGFJPSA-M 0.000 description 1
- JKPSVOHVUGMYGH-UHFFFAOYSA-M sodium;(4,6-dimethoxypyrimidin-2-yl)-[[3-methoxycarbonyl-6-(trifluoromethyl)pyridin-2-yl]sulfonylcarbamoyl]azanide Chemical compound [Na+].COC(=O)C1=CC=C(C(F)(F)F)N=C1S(=O)(=O)NC(=O)[N-]C1=NC(OC)=CC(OC)=N1 JKPSVOHVUGMYGH-UHFFFAOYSA-M 0.000 description 1
- RFOHRSIAXQACDB-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl RFOHRSIAXQACDB-UHFFFAOYSA-M 0.000 description 1
- DHJHUXNTNSRSEX-UHFFFAOYSA-M sodium;2-(4-chloro-2-methylphenoxy)propanoate Chemical compound [Na+].[O-]C(=O)C(C)OC1=CC=C(Cl)C=C1C DHJHUXNTNSRSEX-UHFFFAOYSA-M 0.000 description 1
- AXKBOWBNOCUNJL-UHFFFAOYSA-M sodium;2-nitrophenolate Chemical compound [Na+].[O-]C1=CC=CC=C1[N+]([O-])=O AXKBOWBNOCUNJL-UHFFFAOYSA-M 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PQTBTIFWAXVEPB-UHFFFAOYSA-N sulcotrione Chemical compound ClC1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O PQTBTIFWAXVEPB-UHFFFAOYSA-N 0.000 description 1
- OORLZFUTLGXMEF-UHFFFAOYSA-N sulfentrazone Chemical compound O=C1N(C(F)F)C(C)=NN1C1=CC(NS(C)(=O)=O)=C(Cl)C=C1Cl OORLZFUTLGXMEF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- RJKCKKDSSSRYCB-UHFFFAOYSA-N tebutam Chemical compound CC(C)(C)C(=O)N(C(C)C)CC1=CC=CC=C1 RJKCKKDSSSRYCB-UHFFFAOYSA-N 0.000 description 1
- XQTLDIFVVHJORV-UHFFFAOYSA-N tecnazene Chemical compound [O-][N+](=O)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl XQTLDIFVVHJORV-UHFFFAOYSA-N 0.000 description 1
- IUQAXCIUEPFPSF-UHFFFAOYSA-N tembotrione Chemical compound ClC1=C(COCC(F)(F)F)C(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O IUQAXCIUEPFPSF-UHFFFAOYSA-N 0.000 description 1
- BCQMBFHBDZVHKU-UHFFFAOYSA-N terbumeton Chemical compound CCNC1=NC(NC(C)(C)C)=NC(OC)=N1 BCQMBFHBDZVHKU-UHFFFAOYSA-N 0.000 description 1
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 description 1
- FZXISNSWEXTPMF-UHFFFAOYSA-N terbutylazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C)=N1 FZXISNSWEXTPMF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LOQQVLXUKHKNIA-UHFFFAOYSA-N thifensulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C2=C(SC=C2)C(O)=O)=N1 LOQQVLXUKHKNIA-UHFFFAOYSA-N 0.000 description 1
- IYMLUHWAJFXAQP-UHFFFAOYSA-N topramezone Chemical compound CC1=C(C(=O)C2=C(N(C)N=C2)O)C=CC(S(C)(=O)=O)=C1C1=NOCC1 IYMLUHWAJFXAQP-UHFFFAOYSA-N 0.000 description 1
- DQFPEYARZIQXRM-LTGZKZEYSA-N tralkoxydim Chemical compound C1C(=O)C(C(/CC)=N/OCC)=C(O)CC1C1=C(C)C=C(C)C=C1C DQFPEYARZIQXRM-LTGZKZEYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XOPFESVZMSQIKC-UHFFFAOYSA-N triasulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)OCCCl)=N1 XOPFESVZMSQIKC-UHFFFAOYSA-N 0.000 description 1
- BQZXUHDXIARLEO-UHFFFAOYSA-N tribenuron Chemical compound COC1=NC(C)=NC(N(C)C(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 BQZXUHDXIARLEO-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- KVEQCVKVIFQSGC-UHFFFAOYSA-N tritosulfuron Chemical compound FC(F)(F)C1=NC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(F)(F)F)=N1 KVEQCVKVIFQSGC-UHFFFAOYSA-N 0.000 description 1
- YNWVFADWVLCOPU-MAUPQMMJSA-N uniconazole P Chemical compound C1=NC=NN1/C([C@@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MAUPQMMJSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Prostheses (AREA)
Description
SOSPENSIONI NON ACQUOSE PER IL CONTROLLO DELLA DERIVA
La presente invenzione riguarda sospensioni non acquose, con proprietà di controllo della deriva (drift control), che contengono un veicolo liquido, una sostanza polimerica attiva nel controllo della deriva, un emulsionante e uno specifico agente sospendente; essa è inoltre relativa a un metodo per la preparazione e a un metodo per l’utilizzo di tali sospensioni non acquose.
STATO DELL’ARTE
In agricoltura si spruzzano frequentemente sulle piante e nel loro habitat circostante formulazioni di composti attivi, normalmente diluiti in un liquido acquoso. Quando si applicano queste formulazioni, si osserva un più o meno marcato fenomeno di deriva della soluzione spray che contiene le sostanze attive.
La deriva dello spruzzo (spray drift) implica materiale che non raggiunge l’obiettivo durante l’applicazione: esso rappresenta un fattore limitante che riduce l'efficienza dei trattamenti pesticidi, aumentando di conseguenza i loro costi. Inoltre aumenta l'impatto dei prodotti chimici sull'ambiente e può avere un effetto negativo sulle piante non facenti parte dell’obiettivo del trattamento.
Inoltre lo spray drift può inquinare i corsi di acqua adiacenti all’obiettivo, l'acqua della falda freatica, aree naturali e terreni boscosi. Lo spray drift può esporre l'applicatore e parte della popolazione al contatto con prodotti chimici potenzialmente nocivi o comunque sgradevoli.
Lo spray drift è provocato da una combinazione di fattori quali velocità del vento, condizioni atmosferiche locali, tipo di ugello, pressione dello spruzzatore, velocità del veicolo, altezza operativa dello spruzzatore e fattori chimici.
La ricerca si è sinora principalmente focalizzata sulla riduzione dello spray drift mediante modifica delle caratteristiche dello spruzzatore, quali il tipo di ugelli e la pressione operativa, e mediante l’uso di speciali coadiuvanti, noti come agenti di controllo della dispersione (agenti anti-drift), in grado di ottimizzare la distribuzione dimensionale delle goccioline, riducendo il numero di quelle più piccole e limitando l’accrescimento di quelle più grandi.
Gli agenti anti-drift modificano le proprietà viscoelastiche del liquido spruzzato, più specificamente la viscosità elongazionale, e la sua tendenza a separare in goccioline più piccole. Questi fattori danno luogo a uno spruzzo con una ridotta percentuale di goccioline fini, cioè di quelle che hanno diametro sotto i 150 micron.
Guar e guar derivati sono tra i più comuni agenti di controllo della deriva (agenti anti-drift) e venivano utilizzati tradizionalmente in forma solida aggiungendoli come tali alla formulazione acquosa agrochimica prima dell’applicazione a spruzzo (“in tank”). Tuttavia, l’idratazione di polimeri idrosolubili quali il guar e i suoi derivati, in polvere o granuli, nei mezzi acquosi può risultare spesso un compito arduo e frustrante. Una dispersione insufficiente del guar in polvere, causata spesso da un’aggiunta troppo veloce della polvere al mezzo acquoso o da agitazione insufficiente del mezzo, causa spesso la formazione di agglomerati, o grumi. La formazione di grumi produce difficoltà nell’applicazione a spruzzo e la perdita di efficienza nel controllo della deriva, poiché causa un abbassamento della concentrazione del guar effettivamente disciolto nel mezzo. In aggiunta, il mezzo acquoso potrebbe risultare difficilmente pompabile, e verificarsi il rischio di ostruzione degli ugelli di spruzzo.
Per superare gli svantaggi associati all’uso di composizioni in polvere a base guar per il controllo della deriva, l’utilizzo di composizioni liquide concentrate contenenti guar, acquose o a base olio, rappresenta una soluzione promettente e in parte già praticata nel settore.
Nell’arte nota, US 6,939,555 descrive ad esempio una composizione per uso in agricoltura che contiene un fertilizzante o un olio e almeno una farina di origine naturale come agente coadiuvante della deposizione. Simili composizioni, tuttavia, mostrano una tendenza a sedimentare nel tempo, come riportato in Halecky, A., Roberts, J., Penfield, K., and Baker, T., "Evaluation of a Modified Guar OD Formulation for Spray Drift Mitigation," Journal of ASTM International, Vol.8, No. 10, 2011, pp. 1-13.
AU 2013206347 descrive un concentrato liquido a base olio che contiene: a) circa 0.01-15% in peso di un additivo che modifica la viscosità di un liquido spruzzabile (un agente anti-drift); b) circa 56-75 % in peso di un olio scelto tra gli oli vegetali, le paraffine, gli oli minerali e sintetici o le loro miscele; e c) circa 1-5% in peso di un agente disperdente.
US 2011/0054042 descrive una composizione di guar non-acquosa che contiene polietilene glicol, un olio vegetale, un emulsionante e un’argilla come agente sospendente.
Nonostante ciò, sussiste ancora la necessità di fornire composizioni non acquose che contengano guar o derivati di guar o altri agenti anti-drift, che siano stabili, diano la desiderata azione anti-deriva, e, possibilmente, permettano di veicolare altri additivi, quali condizionanti, emulsionanti e coadiuvanti (adjuvant), nella composizione agrochimica finale.
RIASSUNTO DELL'INVENZIONE
È pertanto oggetto della presente invenzione una sospensione non acquosa contenente:
a) da 20 a 90% in peso di un veicolo scelto dal gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele;
b) da 2 a 60% in peso di un polimero solubile in acqua disperso nel veicolo, il polimero solubile in acqua essendo scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele;
c) da 0,5 a 15% in peso di un agente sospendente costituito da un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico;
d) da 1 a 20% in peso di un emulsionante.
Un ulteriore oggetto dell'invenzione è un metodo per ridurre la deriva delle goccioline durante l’applicazione a spruzzo di formulazioni pesticida, o di formulazioni per la cura delle colture, che comprende miscelare la formulazione prima dell’applicazione con una sospensione non acquosa che contiene:
a) da 20 a 90% in peso di un veicolo scelto dal gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele;
b) da 2 a 60% in peso di un polimero solubile in acqua disperso nel veicolo, il polimero solubile in acqua essendo scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele;
c) da 0,5 a 15% in peso di un agente sospendente costituito da un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico;
d) da 1 a 20% in peso di un emulsionante,
e spruzzare la formulazione sul campo.
Secondo un'altra forma di realizzazione, l'invenzione fornisce un metodo per la preparazione di una sospensione non-acquosa che comprende le seguenti fasi:
i. preparare da 20 a 90% in peso di un veicolo scelto nel gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele;
ii. preparare da 2 a 60% in peso di un polimero solubile in acqua scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele;
iii. preparare da 1 o 20% in peso di un emulsionante;
iv. miscelare il veicolo, il polimero solubile in acqua e l’emulsionante, in qualsiasi ordine e regolare, se necessario, il pH della miscela risultante, misurata all’1% in peso in acqua, portandolo tra 3 e 6 mediante l’aggiunta di un acido;
v. aggiungere alla miscela ottenuta da 0,5 a 15% in peso di un agente sospendente costituito da un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico.
DESCRIZIONE DETTAGLIATA DELL'INVENZIONE
Preferibilmente, la suddetta sospensione non acquosa comprende:
a) da 5 a 20% in peso di un veicolo scelto dal gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele;
b) da 5 a 20% in peso di un polimero solubile in acqua disperso nel veicolo, il polimero solubile in acqua essendo scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele;
c) da 1 a 10% in peso di un agente sospendente, che è un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico;
d) da 3 a 20% in peso di un emulsionante.
Sebbene in letteratura siano state descritte sospensioni non acquose contenenti vari agenti di sospendenti, si è sorprendentemente trovato che anche copolimeri di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico possono essere impiegati con successo per fornire sospensioni non acquose di un polimero solubile in acqua che siano stabili e facilmente versabili. Questo risultato è particolarmente sorprendente, in quanto tali copolimeri, che in genere sono ottenuti attraverso un processo di polimerizzazione in emulsione, sono stati sviluppati e sono diffusamente utilizzati come addensanti e/o agenti sospendenti in sistemi acquosi (ad esempio in prodotti cosmetici o detergenti), in cui il loro effetto addensante è dovuto alla repulsione elettrostatica tra i gruppi carbossilati generati in ambiente acquoso basico.
Le sospensioni secondo l'invenzione sono non-acquose. Nel presente documento, con "non-acquoso" s’intende un liquido sostanzialmente privo di acqua o che contiene una quantità piccola di acqua. La quantità piccola di acqua nel mezzo di sospensione può derivare da diverse fonti: il tenore di umidità del polimero idrosolubile, la quantità residua di acqua che può essere presente nel veicolo non-acquoso in seguito a un processo di distillazione, il contenuto d'acqua del copolimero, che può essere fornito sotto forma di emulsione. Detta quantità piccola di acqua è tipicamente inferiore al 10% in peso, preferibilmente è inferiore al 7% in peso della sospensione.
I veicoli dell'invenzione sono non-acquosi e sono miscibili con acqua. Veicoli adatti sono scelti dal gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele. Preferibilmente, detti veicoli non acquosi sono glicol eteri.
I glicoli o i poliglicoli adatti per essere utilizzati come veicolo dell'invenzione dovrebbero avere un peso molecolare superiore a 100 Da; composti aventi pesi molecolari inferiori a 100 Da tendono a solubilizzare in maniera indesiderata le particelle sospese. Tuttavia, a causa del requisito che il veicolo sia nella fase liquida a temperature ambiente, il loro peso molecolare dovrebbe essere inferiore a 4.000 Da. Pertanto, glicoli e poliglicoli adatti possono avere un peso molecolare compreso tra 100 e 4000 Da, preferibilmente da 100 a 2000 Da, e più preferibilmente da circa 100 a 1000 Da, ancora più preferibilmente tra 200 e 500 Da (i pesi molecolari dei veicoli ossidrilati sono calcolati in base al numero di idrossile, che può essere determinato secondo i metodi standard ASTM E222-10 o E1899-16). I glicoli utilizzabili come veicolo hanno la seguente formula generale:
H-O-R1-O-H,
dove R1 è un gruppo alchilenico avente da 4 a 8 atomi di carbonio. Esempi di glicoli adatti includono 1,5-pentandiolo ed esilenglicole.
I poliglicoli che possono essere usati come veicolo hanno la seguente formula:
H-[O-R1]n-O-H,
dove R1 è un gruppo alchilenico avente da 1 a 6 atomi di carbonio, preferibilmente da 2 a 4 atomi di carbonio. Il valore per n è un intero compreso tra 1 e 100. Esempi specifici di poliglicoli che possono essere utilizzati in modo appropriato comprendono, senza essere limitati ad essi, trietilenglicole, dipropilenglicole, tripropilenglicole, polietilenglicole (avente un peso molecolare compreso tra 200 e 4000 Da, preferibilmente da 200 a 1.000 Da) e polipropilene glicole (avente un peso molecolare compreso tra 200 e 4000 Da, preferibilmente da 200 a 1000 Da). I poliglicoli preferiti per l'impiego come veicolo sono polietilene glicol e trietilenglicole.
I glicol eteri che possono essere usati come veicolo hanno la seguente formula generale:
R2-[O-R1]n-O-R3,
dove R1 è un gruppo alchilenico contenente da 1 a 6 atomi di carbonio, preferibilmente da 2 a 4 atomi di carbonio, e dove ciascun R<2 >e R<3 >può essere un idrogeno, un gruppo alchile, arile, aralchile o alchilarile contenente da 1 a 10 atomi di carbonio, purché non siano entrambi idrogeno. Il valore di n è un intero compreso nell'intervallo da 1 a 10. Esempi specifici di glicol eteri che possono essere appropriatamente utilizzati come veicolo comprendono, senza essere limitati ad essi, etilenglicole butil etere, dietilenglicole dimetil etere, dietilenglicole etil etere, dietilenglicole butil etere (butil diglicol), dietilenglicole fenil etere, trietilenglicol butil etere, dipropilenglicole metil etere e dipropilenglicole dimetil etere. I glicol eteri preferiti da impiegare come veicoli delle sospensioni sono monoalchil glicoli eteri e, in particolare, dipropilenglicole metil etere e dietilenglicole butil etere, il dietileneglicole butil etere essendo più preferito.
Gli esteri di glicoli che possono essere usati come veicolo hanno la seguente formula generale:
R1-COO-[R2-O]n-R3,
dove R1 è un gruppo alchile avente da 1 a 6 atomi di carbonio, preferibilmente da 1 a 4 atomi di carbonio, e dove R2 è un gruppo alchile avente da 1 a 6 atomi di carbonio, preferibilmente da 1 a 4 atomi di carbonio e dove R3 è un idrogeno, alchile o OOCR4, dove R4 ha lo stesso significato di R1. Il valore di n è un intero compreso nell'intervallo da 1 a 10. Esempi specifici di esteri di glicoli che possono essere appropriatamente utilizzati come veicolo comprendono, ma senza essere limitati ad essi, 1,2-etandiolo monoacetato ed etilenglicol diacetato.
Altri esempi di esteri di glicoli che possono essere appropriatamente utilizzati come veicolo comprendono, ma senza essere limitati ad essi, 2-etossi etilacetato, dietilenglicol etil etere acetato, dietilenglicol butil etere acetato e dipropilenglicole metil etere acetato.
Esteri di lattati adatti ad essere utilizzati come veicolo comprendono, ma senza essere limitati ad essi, etil lattato, metil lattato, butil lattato e loro combinazioni.
Secondo l'invenzione, i veicoli più preferiti sono i glicol eteri e in particolare l'etilenglicole butil etere, il dietilenglicole butil etere, il trietilenglicole butil etere e il dipropilenglicole metil etere, il dietilenglicole butil etere essendo preferito.
Le sospensioni liquide non acquose che sono considerate stabili secondo l'invenzione sono quelle in cui il polimero solubile in acqua rimane disperso nella fase liquida e non si ha separazione di fasi dopo stoccaggio per 14 giorni a 54 °C o quelle sospensioni che si separano, ma mostrano una separazione di fase liquida nella parte superiore della sospensione che è inferiore al 5% in volume dopo la conservazione per 14 giorni a 50 °C.
Secondo l'invenzione, il polimero solubile in acqua è sotto forma di particolato solido sostanzialmente insolubile o solo parzialmente solubile nel veicolo non-acquoso. Il diametro medio delle particelle di polimero è compreso tra circa 0,1 e circa 1000 micron, preferibilmente da circa 0,5 a circa 500 micron, più preferibilmente da circa 1 a circa 100 micron.
Secondo l'invenzione, i polimeri idrosolubili adatti comprendono vari polisaccaridi noti o loro derivati.
Il termine "polisaccaride", per come è utilizzato in questo testo, indica un polimero comprendente una pluralità di monosaccaridi (unità di zucchero), tipicamente pentosi o esosi. Esempi non limitativi di polisaccaridi idonei comprendono amidi, cellulose, emicellulose, xilani, xiloglucani, chitina, poligalattomannani, poliarabinani, poligalattani e loro miscele. Il termine "polisaccaride" è utilizzato anche per includere polimeri con eteroatomi presenti nella struttura polisaccaridica, come chitina e/o chitosano o polimeri che comprendono diversi tipi di unità di zucchero (eteropolisaccaridi), ad esempio polimeri che comprendono contemporaneamente pentosi e esosi.
Con il termine "derivati di polisaccaridi" s’intendono polisaccaridi modificati con reazioni chimiche ovvero che contengono gruppi chimici legati covalentemente al polisaccaride tramite sintesi chimica, ad esempio gruppi metilici, etilici, carbossimetilici, idrossietilici, idrossipropilici, cationici, catene alchiliche idrofobizzanti e simili.
Questi polisaccaridi e i loro derivati sono noti nello stato dell’arte e sono commercialmente disponibili o possono essere prodotti utilizzando metodi ben noti nello stato dell’arte.
Esempi idonei e non limitativi di polisaccaridi includono poligalattomannani, xantano, chitosano, xiloglucani, pectina, alginato, agar, destrina, amido, amilosio, amilopectina, alternano, gellano, mutano, destrano, pullulano, fruttano, gomma arabica e carragenina.
Esempi di polgalattomannani adatti sono guar (“guar gum” o farina di guar), farina di semi di carrube, farina di tara, farina di cassia e farina di sesbania. Un esempio adatto di xiloglucano è la farina di tamarindo.
Fra i derivati di polisaccaridi, esempi di derivati di cellulosa sono l'idrossietil cellulosa, l'etilidrossietil cellulosa, la metilcellulosa, l'etil cellulosa, la metil idrossipropil cellulosa, la carbossimetilmetil cellulosa, la carbossimetil cellulosa idrofobicamente modificata, l'idrossietil cellulosa idrofobicamente modificata, l’idrossipropil cellulosa idrofobicamente modificata, la metil cellulosa idrofobicamente modificata.
I derivati di guar che sono utili in questa forma di realizzazione preferita includono carbossimetil guar, idrossietil guar, idrossipropil guar, carbossimetilidrossipropil guar, guar cationico, idrossipropil guar cationico, guar idrfobicamente modificato, carbossimetil guar idrofobicamente modificato, idrossietil guar idrofobicamente modificato, idrossipropil guar idrofobicamente modificato, idrossipropil guar cationico idrofobicamente modificato, carbossimetilidrossipropil guar idrofobicamente modificato, guar cationico idrofobicamente modificato.
Esempi di derivati dell'amido comprendono carbossimetil amido e idrossipropil amido.
Altri polisaccaridi possono essere derivatizzati allo stesso modo.
I polisaccaridi o i loro derivati dell'invenzione possono essere reticolati, utilizzando, ad esempio, borace (tetraborato di sodio) o gliossale.
Secondo una forma di realizzazione dell'invenzione, i polisaccaridi derivatizzati hanno un grado di sostituzione (DS) nell'intervallo 0,01-3,0 o una sostituzione molare (MS) compresa tra 0,01 e 4,0.
L'espressione "grado di sostituzione" (DS) si riferisce al numero medio di siti che sono sostituiti da un gruppo funzionale (per esempio, carbossimetil) per unità anidroglicosidica nel polisaccaride. Di solito, ognuna delle unità anidroglicosidiche di un polisaccaride contiene in media tre siti idrossilici disponibili. Un grado di sostituzione di tre significa che tutti i siti idrossilici disponibili sono stati sostituiti da gruppi funzionali.
Con l'espressione "sostituzione molare" (MS) s’intende il numero di sostituenti (ad esempio, idrossipropil) su ciascuna unità anidroglicosidica del polisaccaride.
Secondo una realizzazione preferita dell’invenzione, il polimero solubile in acqua è guar o un suo derivato.
Il guar (o farina di guar) è un polisaccaride della famiglia dei poligalattomannani e viene estratto da una leguminosa, “Cyamopsis Tetragonolobus”, che cresce nelle regioni semi desertiche in paesi tropicali, in particolare in India e in Pakistan, e ha rapporto circa 2:1 tra le unità di D-mannosio e D-galattosio.
Tipicamente ha peso molecolare medio ponderale tra 2.000.000 e 5.000.000 Da.
Il polimero solubile in acqua è più preferibilmente guar o idrossipropil guar, ancora più preferibilmente guar.
L'agente sospendente secondo l'invenzione viene utilizzato non solo per fornire una viscosità supplementare al veicolo, ma anche per contribuire a mantenere il particolato non solubile disperso nel veicolo. L'agente sospendente secondo l'invenzione dev’essere solubile nel veicolo della composizione inventiva e nello stesso tempo deve consentire di migliorare la sospendibilità del polimero solubile in acqua nella fase liquida della composizione e quindi la stabilità della composizione inventiva. Sì è trovato che sospensioni non acquose stabili possono essere ottenute utilizzando come agente sospendente un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico.
Preferibilmente, detto copolimero viene ottenuto mediante polimerizzazione di:
a) da 20 a 70% in peso, preferibilmente da 20 a 50% in peso di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico;
b) da 20 a 70% in peso, preferibilmente da 40 a 70% in peso, di un estere di un acido (met)acrilico;
c) da 0 a 3% in peso, preferibilmente da 0,01 a 1% in peso, di un monomero polietilenicamente insaturo;
d) da 0 a 10% in peso, preferibilmente da 0 a 3% in peso di un monomero associativo acrilico non ionico,
in cui la somma di a) e b) rappresenta almeno l'80% in peso della miscela di monomeri.
Detto copolimero può essere preparato secondo metodi di polimerizzazione noti quali polimerizzazione in emulsione, in soluzione, in massa o per precipitazione, ma preferibilmente viene preparata mediante polimerizzazione in emulsione.
Il monomero monoetilenicamente insaturo a) contenente un gruppo carbossilico utile per la preparazione del copolimero della presente invenzione può essere scelto tra acidi mono- o di-carbossilici etilenicamente insaturi o loro sali o loro anidridi, come ad esempio acido acrilico, acido metacrilico, acido itaconico, acido crotonico, acido maleico e acido fumarico. L'acido metacrilico è preferito come monomero monoetilenicamente insaturo contenente un gruppo carbossilico a).
L'estere di un acido (met)acrilico b) è scelto tra gli alchil esteri C1-C8 di un acido met(acrilico), come metil, etil, propil, butil, 2-etilesil (met)acrilati o loro miscele. Preferibilmente l'estere di acido (met)acrilico b) è etil acrilato. Il monomero c) polietilenicamente insaturo può essere uno qualsiasi dei derivati polifunzionali noti per essere utilizzati nella polimerizzazione radicalica con monomeri (met)acrilici. Tra i monomeri polietilenicamente insaturi adatti ci sono trimetilolpropano triacrilato, diallil maleato, allil metacrilato, diallil ftalato, N-metilene-bisacrilammide, pentaeritritol eteri poliacrilati e triallil cianuro.
Il monomero associativo acrilico non ionico d) può essere scelto tra esteri di un acido (met)acrilico con un idrocarbil monoetere alchilico, alchilarilico o policiclico C8-C30 di un polietilenglicole avente almeno due unità di ossietilene, preferibilmente da 10 a 40 unità di ossietilene e fino a 70 unità di ossietilene; questi esteri hanno formula generale
H2C=C(R)-CO-O-(CH2CH2O)n-R',
dove
R è H oppure CH3, con quest'ultimo preferito;
n è almeno 2 e preferibilmente ha un valore medio di almeno 10, fino a 40 a 60 o fino a 70;
e R' è un gruppo idrofobico, ad esempio alchile, alchilarile o policiclico alchilico avente da 8 a 30 atomi di carbonio, avente preferibilmente in media da 12 a 18 atomi di carbonio.
Altri monomeri insaturi possono essere utilizzati nella polimerizzazione accanto ai monomeri da a) a d), come ad esempio altri monomeri acrilici non ionici, monomeri monoetilenicamente insaturi eventualmente contenenti un gruppo acido solfonico, monomeri acrilici cationici. Esempi non limitanti di altri monomeri insaturi utilizzabili sono acetato di vinile, stirene, cloruro di vinile, cloruro di vinilidene, acrilonitrile, (met)acrilammide, N,N-dimetil(met)acrilammide, t-butil(met)acrilammide, acido 2-acrilammido-2-metilpropan solfonico.
Il copolimero dell'invenzione ha una viscosità Brookfield<® >in acqua a pH 7,5 (RVT, 20 rpm, 1,0% in peso a 20 °C) compresa tra circa 500 e circa 10000 mPa*s. ;Sorprendentemente, il copolimero dell'invenzione mostra il suo effetto sospendente ottimale se è completamente indissociato (cioè, quando i gruppi carbossilici sono protonati). Per questo motivo, se il polimero solubile in acqua da sospendere ha una basicità residua, o qualche altro componente porta basicità nella composizione, può essere necessario aggiungere un acido prima di aggiungere l’agente sospendente alla composizione, per regolarne il pH, misurato all’1% in peso in acqua, tra 3 e 6, preferibilmente tra 4 e 5. ;Facoltativamente, le sospensioni dell'invenzione possono contenere da 0 a 2,0% in peso di agenti sospendenti aggiuntivi scelti tra silice, silice pirogenica, argille colloidali o non colloidali come smecticti o attapulgiti. Le smectiti adatte (note anche come argille montmorillonoidi) includono, ad esempio, montmorillonite (bentonite), volchonskoite, nontronite, beidellite, hectorite, saponite, sauconite e vermiculite. ;Le attapulgiti (note anche come palygorskiti) sono argille ricche di magnesio e gli esempi idonei sono quelli commercialmente disponibili da BASF con il marchio Attagel® e da Elementis Specialties con il marchio Baragel®. ;L’emulsionante nella sospensione liquida non-acquosa dell’invenzione è tipicamente costituito da un tensioattivo anionico, non-ionico, cationico, amfolitico o da una loro miscela. ;Emulsionanti adatti sono ad esempio, tensioattivi non-ionici quali: alcol alifatici saturi o insaturi polialcossilati, preferibilmente polietossilati, aventi da 8 a 24 atomi di carboni nella catena alchilica, che deriva dal corrispondente acido grasso o da prodoti petrolchimici, e aventi da 1 a 100, preferibilmente da 4 a 40, unità da ossido di etilene (EO); arilalchilfenolii polialcossilati, preferibilmente polietossilati, quali ad esempio, tristirilfenoli aventi un grado di etossilazione media tra 8 e 80, preferibilmente tra 16 e 40; alchilfenoli polialcossilati, preferibilmente polietossilati, aventi uno o più radicali alchilici, quali ad esempio, nonil fenolo o tri-sec-butil fenolo, e un grado di etossilazione tra 2 e 40, preferibilmente tra 4 e 20; idrossiacidi grassi o gliceridi di idrossiacidi grassi alcossilati, preferibilmente polietossilati, per esempio olio di ricino, avente grado di etossilazione tra 10 e 80; sorbitan o sorbitol esteri con acid grassi, o loro polialcossilati, preferibilmente polietossilati; ammine grasse polialcossilate, preferibilmente polietossilate; copolimeri a due o tre blocchi, per esempio da alchilene ossidi, per esempio da ossido di etilene e ossido di propilene, aventi peso molecolare medio tra 200 and 8000 g/mol, preferibilmente tra 1000 e 4000 g/mol; alchilpoliglicosidi o loro derivati polialcossilati, preferibilmente loro derivati polietossilati. ;Gli emulsionanti non-ionici preferiti sono alcoli polietossilati, preferibilmente da fonte rinnovabile, quali alcoli naturali C12-C14 etossilati 4-8 moli (4-8 EO); gliceridi di idrossiacidi grassi polietossilati, ammine grassi polietossilate, tipicamente ammine primarie C12-C22 polietossilate, e copolimeri a blocchi polietilene ossido/ polipropilene ossido. ;Sono anche utili come emulsionanti i tensioattivi anionici, che fungono anche un’azione bagnante, per esempio: tensioattivi polialcossilati, preferibilmente polietossilati, che sono modificati ionicamente mediante conversione di una funzione ossidrilica terminale dell’ossido di alchilene in estere solfato o fosfato; sali di metalli alcalini o alcalino terrosi di acidi alchilarilsolfonici aventi una catena alchilica lineare o ramificata; sali di metalli alcalini o alcalino terrosi di paraffine solfonate e paraffine clorurate e solfonate; polielettroliti, quali lignosolfonati, condensati di naftalen solfonati e formaldeide, polistirenesolfonati o polimeri solfonati insaturi o aromatici; esteri anionici di alchilpoliglicosidi, quali quelli descritti in WO 2010/100039, per esempio alchilpoliglicosidi solfosuccinati o citrati; solfosuccinati che sono mono- o di-esterificati con alcoli lineari o ramificati, alifatici, cicloalifatici o aromatici, o solfosuccinati mono- o di-esterificati con addotti di addotti di alcoli con polialchileneossidi. I tensioattivi anionici preferiti sono dialchil C4-C14 solfocuccinati, in particolare diottilsolfosuccinato. ;Esempi di emulsionanti cationici e anfolitici sono sali di ammonio quaternario, alchil amminoacidi, betaine o imidazoline anfolitiche. ;Preferibilmente, gli emulsionanti sono una miscela di tensioattivi non-ionici e anionici, più preferibilmente una miscela di almeno un tensioattivo nonionico scelto tra gli alcoli polietossilati, preferibilmente da fonte rinnovabile, quali alcoli naturali C12-C14 etossilati 4-8 moli (4-8 EO); gliceridi di idrossiacidi grassi polietossilati, ammine grassi polietossilate, tipicamente ammine primarie C12-C22 polietossilate e copolimeri a blocchi polietilene ossido/ polipropilene ossido, in miscela con almeno un dialchil solfosuccinato C4-C14. ;L’emulsionante più preferito è una misceal di alcol C12-C14 (4-8 EO) e diottil solfosuccinato. ;La presente invenzione è anche relativa a un metodo per ridurre la deriva delle goccioline durante l’applicazione a spruzzo di formulazioni pesticida, o di formulazioni per la cura delle colture, che comprende miscelare la formulazione prima dell’applicazione con la sospensione non acquosa per il controllo della deriva sopra descritta. ;Quando la composizione che deve essere spruzzata è una formulazione per la cura delle colture, secondo alcuni aspetti, essa è una formulazione fertilizzante che contiene come sostanza attiva, ad esempio: sali di ammonio, quali solfato di ammonio, ammonio bisolfato, sali di ammonio di acidi carbossilici, cloruro di ammonio, ammonio carbonato, ammonio fosfato; urea e derivati dell’urea; fonti di fosfati quali acidi fosforici e loro sali; fonti di potassio, quali potassio mono- o di- fosfato, potassio carbonato, potassio citrato, potassio nitrato; composti contenenti micronutrienti e nutrienti secondari, quali zinco, manganese, magnesio, ferro, calcio, zolfo, boro, ecc.; loro miscele. ;Quando la formulazione è una formulazione pesticida, secondo alcuni aspetti preferiti, è una formulazione erbicida, che contiene un erbicida quale sostanza attiva. L’erbicida può essere: Acetochlor, Acibenzolar, Acibenzolar-S-metil, Acifluorfen, Sodio Acifluorfen, Aclonifen, Alachlor, Allidochlor, Alloxydinn, Sodio Alloxydinn, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, Aminocyclopyrachlor, Aminopyralid, Amitrole, Ammonium sulfamat, Ancymidol, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Aziprotryn, Beflubutamid, Benazolin, Etil Benazolin, Bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron, Metil Bensulfuron, Bentazone, Benzfendizone, Benzobicyclon, Benzofenap, Benzofluor, Benzoylprop, Bicyclopyrone, Bifenox, Bispyribac, Bispyribacsodium, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrole, Carbetamide, Carfentrazone, Etil Carfentrazone, Chlomethoxyfen, Chloramben, Chlorazifop, Butil Chlorazifop, Chlorbromuron, Chlorbufam, Chlorfenac, Sodio Chlorfenac, Chlorfenprop, Chlorflurenol, Metil Chlorflurenol, Chloridazon, Chlorimuron, Etil Chlorimuron, Chlormequat-cloruro, Chlornitrofen, Chlorophthalim, Dimetil Chlorthal, Chlorotoluron, Chlorsulfuron, Cinidon, Etil Cinidon, Cinmethylin, Cinosulfuron, Clethodim (C10), Clodinafop, Propargil Clodinafop, Clofencet, Clomazone, Clomeprop, Cloprop, Clopyralid (C1), Cloransulam, Metil Cloransulam, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim (C11), Cycluron, Cyhalofop, Butil Cyhalofop, Cyperquat, Cyprazine, Cyprazole, 2,4-D (e suoi sali o esteri, quali 2,4-D-butotil, 2,4-D-butil, 2,4-D-dimetilammonio, 2,4-D-diolamina, 2,4-D-etil, 2,4-D-etilesil, 2,4-D-isobutil, 2,4-D-isottil, 2,4-D-isopropil, 2,4-D-isopropilammonio, 2,4-D-sodio, 2,4-D-triisopropanolammonio, 2,4-Dtrolamina), 2,4-DB, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP), Diallate, Dicamba (e suoi sali o esteri, quali Dicamba-butotil, Dicamba sale di diglicolamina, Dicamba-dimetilammonio, Dicamba-diolamina, Dicambaisopropilammonio, Potassio Dicamba, Sodio Dicamba, Dicambatrolamina), Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diclofopmetil, Diclofop-P-metil, Diclosulam, Diethatyl, Diethatyl-etil, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Sodio Diflufenzopyr, Dimefuron, Sodio Dikegulac, Dimefuron, Dimepiperate, Dimethachlor (C2), Dimethametryn, Dimethenamid, Dimethenamid-P, Dimethipin, Dimetrasulfuron, Dinitramine, Dinoseb, Dinoterb, Diphenamid, Dipropetryn, Diquat, Diquat-dibromuro, Dithiopyr, Diuron, DNOC, Etil Eglinazine, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethametsulfuronmethyl, Ethephon, Ethidimuron, Ethiozin, Ethofumesate, Ethoxyfen, Etil Ethoxyfen, Ethoxysulfuron, Etobenzanid, F-5331, i.e. N-[2-Cloro-4-fluoro-5-[4-(3-fluoropropil)-4,5-diidro-5-oxo-1H-tetrazol-1-il]-fenl]-etan solfonamide, F-7967, i.e. 3-[7-Cloro-5-fluoro-2-(trifluorometil)-1H-benzimidazol-4-il]-1-metil-6-(trifluormetil)pirimidin-2,4(1H,3H)-dione, Fenoprop, Fenoxaprop, Fenoxaprop-P, Etil Fenoxaprop, Fenoxaprop-P-etil (C3), Fenoxasulfone, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropil, Flamprop-M-metil, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop-butil, Fluazifop-P-butil, Fluazolate, Flucarbazone, Sodio Flucarbazone, Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpyr, Etil Flufenpyr-, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentil, Flumioxazin, Flumipropyn, Fluometuron, Fluorodifen, Fluoroglycofen, Etil Fluoroglycofen, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-metil-sodio, Flurenol, Butil Flurenol, Fluridone, Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet, Metil Fluthiacet, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxyfen, Glufosinate, Ammonio Glufosinate, Glyphosate, Diammonio Glyphosate, Isopropilammonio Glyphosate, Potassio Glyphosate, H-9201, i.e. O-(2,4-Dimetil-6-nitrofeni)-O-etil-isopropil fosforamidotioato, Halosafen, Halosulfuron, Metil Halosulfuron-, Haloxyfop, Haloxyfop-p (C4), Etossietil Haloxyfop-l, Etossietil Haloxyfop-P, Metil Haloxyfop, Metil Haloxyfop-P, Hexazinone, HW-02, i.e. 1-(Dimetossifosforil)-etil(2,4-diclorofenossi)acetato, Imazamethabenz, Metil Imazamethabenz, Imazamox (C9), Imazamox-ammonio, Imazapic, Imazapyr, Imazapyrisopropylammonio, Imazaquin, Imazaquin-ammonio, Imazethapyr, Imazethapyr-ammonio, Imazosulfuron, Inabenfide, Indanofan, Indaziflam, acido Indolacetic (IAA), acido 4-lndol-3-il-butirrico (IBA), lodosulfuron, sodio metil lodosulfuron, loxynil, Ipfencarbazone, Isocarbamid, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, KUH-043, i.e. 3-({[5-(Difluorometil)-1-metil-3-(trifluorometil)-1H-pirazol-4-il]metil}sulfonil)-5,5-dimetil-4,5-diidro-1,2-ossazolo, Karbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, MCPA, MCPB, metil, -etil e -sodio MCPB, Mecoprop, Mecoprop-sodio, Mecoprop-butotil, Mecoprop-P-butotil, Mecoprop-P-dimetiilammonio, Mecoprop-P-2-etilesil, Mecoprop-P-potassio, Mefenacet, Mefluidide, Mepiquat-cloro, Mesosulfuron, Mesosulfuron-metil, Mesosulfuron-metil-Na, Mesotrione, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor (C5), Metazasulfuron, Methazole, Methiopyrsulfuron, Methiozolin, Methoxyphenone, Methyldymron, 1-Methylcyclopropen, Methylisothiocyanat, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulfuronmethyl, Molinate, Monalide, Monocarbamide, Monocarbamidedihydrogensulfat, Monolinuron, Monosulfuron, Monosulfuron-ester, Monuron, MT-128, i.e. 6-Cloro-N-[(2E)-3-cloroprop-2-en-1-il]-5-metill-N-fenilpiridazin-3-amine, MT-5950, i.e. N-[3-Cloro-4-(1-metletil)-fenil]-2-metilpentanamide, NGGC-011, Naproanilide, Napropamide (C6), Naptalam, NC-310, i.e. 4-(2,4-Diclorobenzoil)-1-metil-5-benzilossipirazolo, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Sodio Nitrophenolat (miscela di isomeri), Nitrofluorfen, Nonansäure, Norflurazon, Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paclobutrazol, Paraquat, Paraquat-dichlorid, Pendimethalin, Pendralin, Penoxsulam, Pentanochlor, Pentoxazone, Perfluidone, Pethoxamid, Phenisopham, Phenmedipham, Phenmediphametil, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenop-butil, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazol, Procyazine, Prodiamine, Prifluraline, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Sodio Propoxycarbazone, Propyrisulfuron, Propyzamide, Prosulfalin, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Etil Pyraflufen, Pyrasulfotole, Pyrazolynate (Pyrazolate), Pyrazosulfuron, Pyrazosulfuron-ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-isopropyl, Propil Pyribambenz, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate (C7), Pyriftalid, Pyriminobac, Metil Pyriminobac Pyrimisulfan, Pyrithiobac, Sodio Pyrithiobac, Pyroxasulfone, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Etil Quizalofop, Quizalofop-P, Quizalofop-P-etil, Quizalofop-P-tefuril, Rimsulfuron, Saflufenacil, Secbumeton, Sethoxydim, Siduron, Simazine, Simetryn , SN-106279, i.e. Metil-(2R)-2-({7-[2-cloro-4-(trifluorometil)fenossi]-2-naftil}ossi) propanoate, Sulcotrione, Sulfallate (CDEC), Sulfentrazone, Sulfonneturon, Metil Sulfonneturon, Sulfosate (Glyphosate-trimesium), Sulfosulfuron, SYN-523, SYP-249, i.e. 1-Etossi-3-metil-1-ossobut-3-en-2-il-5-[2-cloro-4-(trifluorometil)fenossi]-2-nitrobenzoate, SYP-300, i.e. 1-[7-Fluoro-3-osso-4-(prop-2-in-1-il)-3,4-diidro-2H-1,4-benzoxazin-6-il]-3-propil-2-tiossoimidazolidin-4,5-dione, Tebutam, Tebuthiuron, Tecnazene, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazafluron, Thiazopyr, Thidiazimin, Thidiazuron, Thiencarbazone, Metil Thiencarbazone, Thifensulfuron, Metil Thifensulfuron, Thiobencarb, Tiocarbazil, Topramezone, Tralkoxydim, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Metil Tribenuron, Acido tricloroacetico (TCA), Triclopyr, Tridiphane, Trietazine, Trifloxysulfuron, Sodio Trifloxysulfuron, Trifluralin (C8), Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapac, Etil Trinexapac, Tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0862, i.e.3,4-Dicloro-N-{2-[(4,6-dimetossipirimidin-2-il)ossi]benzil}anilina, loro Sali e loro miscele. ;Secondo un aspetto preferito, l’invenzione è relativa a un metodo per ridurre la deriva delle goccioline durante l’applicazione a spruzzo di una formulazione pesticida contenente una sostanza attiva erbicida scelta tra Glyphosate, Glufosinate, Paraquat, 2,4-D, Dicamba, Clethodim, loro derivati e/o loro miscele. Quando la sostanza attiva erbicida è una miscela è, preferibilmente, una miscela di Clethodim e Dicamba o una miscela di Dicamba e Glyphosate, o una miscela di Dicamba e Glufosinate. ;Le formulazioni pesticida o per la cura delle colture da applicare sono formulazioni acquose diluite che possono essere spruzzate sui campi. Per gli scopi di questa domanda, il termine "diluito" significa che le formulazioni hanno una concentrazione di sostanze attive da circa 0,001 a circa 50 g/1. Le formulazioni di pesticidi o per la cura delle colture del metodo possono opzionalmente contenere uno o più ingredienti aggiuntivi noti nella tecnica, come condizionanti, agenti chelanti, antiossidanti, agenti antischiuma, riempitivi, agenti umidificanti, agenti disperdenti, agenti distaccanti, agenti regolatori del pH, agenti leganti, stabilizzanti, solventi organici, agenti antigelo, penetranti, bioattivatori o agenti compatibilizzanti. ;L'acqua rappresenta in genere almeno il 90% in peso delle formulazioni acquose diluite. Le formulazioni dei pesticidi o per la cura delle colture sono solitamente preparate in loco dall'agricoltore o dall'imprenditore miscelando formulazioni pesticida concentrate di sostanze attive (che possono essere in varie forme, ad esempio liquidi o polveri puliti, granuli, soluzioni acquose, sospensioni concentrate, emulsioni concentrate, suspoemulsioni o simili), acqua e gli ingredienti supplementari. Le formulazioni diluite qui descritte non richiedono speciali dispositivi di spruzzatura e possono essere applicate sull'area bersaglio utilizzando apparecchiature a spruzzo convenzionali per applicazioni aeree o terrestri, anche con droni droni. ;Per dimostrare i vantaggi della sospensione non acquosa della presente invenzione, sono state preparate sospensioni con agenti sospendenti esemplificativi, valutando il comportamento dell'agente sospendente e la stabilità delle sospensioni così ottenute. ;ESEMPI ;Esempi comparativi11c-3c ;Il veicolo viene pesato in un bicchiere di vetro da 250 ml; il polimero in emulsione viene dosato in una siringa di plastica e viene aggiunto lentamente goccia a goccia sotto agitazione magnetica al veicolo. Dopo 10 minuti di agitazione le particelle del polisaccaride da sospendere vengono pesate e aggiunte lentamente sotto agitazione meccanica al veicolo viscosizzato; la miscela viene agitata per 5 minuti per ottenere una sospensione omogenea. ;Esempio comparativo 4c ed Esempio 5 ;Il veicolo viene pesato in un bicchiere di vetro da 250 ml; l’emulsionante e il guar vengono aggiunti al veicolo sotto agitazione. Si corregge il pH (misurato all’1% in soluzione acquosa) con una soluzione al 50 % di acido citrico, portandolo a 5.5. Il polimero in emulsione viene dosato in una siringa di plastica e viene aggiunto lentamente goccia a goccia sotto agitazione magnetica al veicolo. La miscela viene agitata per circa 10 minuti, fino a ottenere una sospensione omogenea. ;Misure di viscosità ;La viscosità RV Brookfield<® >(20 rpm, 25 °C) delle sospensioni viene misurata seguendo ASTM D 2196 con mandrino 5. ;Prove di stabilità ;200 ml di sospensione vengono versati in una beuta di vetro e chiusi con un tappo per evitare l'evaporazione del fluido. Il vaso è conservato in forno a 54 °C per 14 giorni. La stabilità viene valutata come percentuale di separazione di veicolo sulla sommità della sospensione con la seguente formula: ;% separazione = (altezza di veicolo separato in alto / altezza totale della sospensione) * 100
Una sospensione è considerata stabile se la separazione percentuale dopo 14 giorni a 54 °C è pari o inferiore al 5%.
Le composizioni delle sospensioni (% in peso) e i risultati delle prove sono riportati in Tabella 1.
Non è stato possibile misurare la viscosità degli Esempi comparativi 1c, 2c e 4c a causa della formazione di una pasta al posto di una stabile sospensione.
I risultati del test di stabilità mostrano che il polimero in emulsione secondo l'invenzione è adatto per fornire sospensioni stabili, mentre l’argilla, gli acidi poliacrilici e il polivinilpirrolidone testati negli esempi comparativi non riescono a fornire sospensioni stabili.
Tabella 1
1- comparativo
2-acido poliacrilico reticolato (Guangzhou Tinci Materials Technology Co.,Ltd.) 3-polivinilpirrolidone (Ashland)
4-Baragel®24 (Elementis Specialties), al 10% in peso in dietilene glicol monobutil etere
5-dopo 1 mese a 50°C
nd=pasta, troppo viscosa per essere misurata
Claims (10)
- RIVENDICAZIONI 1. Sospensione non acquosa contenente: a) da 20 a 90% in peso di un veicolo scelto dal gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele; b) da 2 a 60% in peso di un polimero solubile in acqua disperso nel veicolo, il polimero solubile in acqua essendo scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele; c) da 0,5 a 15% in peso di un agente sospendente costituito da un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico; d) da 1 a 20% in peso di un emulsionante.
- 2. La sospensione non acquosa secondo la rivendicazione 1, in cui l'agente sospendente è un copolimero ottenuto per polimerizzazione di: I. da 20 a 70% in peso di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico; II. da 20 a 70% in peso di un estere di un acido (met)acrilico; III. da 0 a 3% in peso di un monomero polietilenicamente insaturo; IV. da 0 a 10% in peso di un monomero acrilico associativo non ionico, in cui la somma di a) e b) rappresenta almeno l'80% in peso della miscela monomerica.
- 3. La sospensione non acquosa secondo la rivendicazione 1, in cui l'agente sospendente è un copolimero ottenuto per polimerizzazione di: I. da 20 a 50% in peso di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico; II. da 40 a 70% in peso di un estere di un acido (met)acrilico; III. da 0,01 a 1% in peso di un monomero polietilenicamente insaturo; IV. da 0 a 3% in peso di un monomero acrilico associativo non ionico, in cui la somma di a) e b) rappresenta almeno l'80% in peso della miscela monomerica.
- 4. La sospensione non acquosa secondo la rivendicazione 1, in cui il polimero solubile in acqua è scelto tra guar e idrossipropil guar.
- 5. La sospensione non acquosa secondo la rivendicazione 1, in cui il veicolo è un glicol etere.
- 6. La sospensione non acquosa secondo la rivendicazione 5, in cui il veicolo è etilenglicole butil etere, dietilenglicole butil etere, trietilenglicole butil etere o dipropilenglicole metil etere.
- 7. La sospensione non acquosa secondo la rivendicazione 6, in cui il veicolo è dietilenglicole butil etere.
- 8. La sospensione non acquosa secondo la rivendicazione 1, che comprende: a) da 50 a 80% in peso di veicolo; b) da 5 a 20% in peso di polimero solubile in acqua; c) da 1 a 10% in peso di agente sospendente; d) da 3 a 20% in peso di emulsionante.
- 9. Metodo per ridurre la deriva delle goccioline durante l’applicazione a spruzzo di formulazioni pesticida, o di formulazioni per la cura delle colture, che comprende miscelare la formulazione prima dell’applicazione con una sospensione non acquosa secondo una qualunque delle rivendicazioni da 1 a 8 e spruzzare la formulazione sul campo.
- 10. Metodo per la preparazione di una sospensione non-acquosa che comprende le seguenti fasi: i. preparare da 20 a 90% in peso di un veicolo scelto nell gruppo costituito da glicoli, poliglicoli, glicol eteri, esteri di glicoli, esteri di lattato o loro miscele; ii. preparare da 2 a 60% in peso di un polimero solubile in acqua scelto tra polisaccaridi, derivati di polisaccaridi e loro miscele; iii. preparare da 1 o 20% in peso di un emulsionante; iv. miscelare il veicolo, il polimero solubile in acqua e l’emulsionante, in qualsiasi ordine e regolare, se necessario, il pH della miscela risultante, misurato all’1% in peso in acqua, portandolo tra 3 e 6, mediante l’aggiunta di un acido; v. aggiungere alla miscela ottenuta da 0,5 a 15% in peso di un agente sospendente costituito da un copolimero di un monomero monoetilenicamente insaturo contenente un gruppo carbossilico e un estere di un acido (met)acrilico.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT102019000006358A IT201900006358A1 (it) | 2019-04-24 | 2019-04-24 | Sospensioni non acquose per il controllo della deriva |
AU2020261248A AU2020261248A1 (en) | 2019-04-24 | 2020-04-23 | Non-aqueous drift control suspensions |
CN202080031370.5A CN113784620B (zh) | 2019-04-24 | 2020-04-23 | 非水性漂移控制悬浮液 |
EP20723303.2A EP3958677A1 (en) | 2019-04-24 | 2020-04-23 | Non-aqueous drift control suspensions |
US17/604,133 US20220192186A1 (en) | 2019-04-24 | 2020-04-23 | Non-aqueous drift control suspensions |
PCT/EP2020/061398 WO2020216872A1 (en) | 2019-04-24 | 2020-04-23 | Non-aqueous drift control suspensions |
BR112021019395A BR112021019395A2 (pt) | 2019-04-24 | 2020-04-23 | Suspensão não aquosa, e, métodos para reduzir a impulsão de pulverização e para preparar uma suspensão não aquosa |
KR1020217038385A KR20220004122A (ko) | 2019-04-24 | 2020-04-23 | 비수성 드리프트 방지 현탁액 |
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IT102019000006358A IT201900006358A1 (it) | 2019-04-24 | 2019-04-24 | Sospensioni non acquose per il controllo della deriva |
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IT201900006358A1 true IT201900006358A1 (it) | 2020-10-24 |
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IT102019000006358A IT201900006358A1 (it) | 2019-04-24 | 2019-04-24 | Sospensioni non acquose per il controllo della deriva |
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US (1) | US20220192186A1 (it) |
EP (1) | EP3958677A1 (it) |
KR (1) | KR20220004122A (it) |
CN (1) | CN113784620B (it) |
AU (1) | AU2020261248A1 (it) |
BR (1) | BR112021019395A2 (it) |
IT (1) | IT201900006358A1 (it) |
WO (1) | WO2020216872A1 (it) |
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IT202100028046A1 (it) | 2021-11-03 | 2023-05-03 | Lamberti Spa | Sospensioni di asfaltite a base solvente |
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US6939555B2 (en) | 2000-01-21 | 2005-09-06 | Helena Holding Company | Manufacture and use of an deposition aid |
WO2010100039A2 (en) | 2009-03-03 | 2010-09-10 | Lamberti Spa | Adjuvant compositions for herbicides |
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EP2536786B1 (en) * | 2010-02-18 | 2015-12-30 | Dow Corning Corporation | Surface-modified hydrogels and hydrogel microparticles |
US9540473B2 (en) * | 2013-03-13 | 2017-01-10 | Akzo Nobel Chemicals International B.V. | Rheology modifiers |
CN107484767A (zh) * | 2017-08-14 | 2017-12-19 | 江苏龙灯化学有限公司 | 一种油基悬浮剂及其制备方法和用途 |
-
2019
- 2019-04-24 IT IT102019000006358A patent/IT201900006358A1/it unknown
-
2020
- 2020-04-23 WO PCT/EP2020/061398 patent/WO2020216872A1/en unknown
- 2020-04-23 BR BR112021019395A patent/BR112021019395A2/pt unknown
- 2020-04-23 AU AU2020261248A patent/AU2020261248A1/en active Pending
- 2020-04-23 US US17/604,133 patent/US20220192186A1/en active Pending
- 2020-04-23 KR KR1020217038385A patent/KR20220004122A/ko unknown
- 2020-04-23 EP EP20723303.2A patent/EP3958677A1/en active Pending
- 2020-04-23 CN CN202080031370.5A patent/CN113784620B/zh active Active
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US6939555B2 (en) | 2000-01-21 | 2005-09-06 | Helena Holding Company | Manufacture and use of an deposition aid |
WO2010100039A2 (en) | 2009-03-03 | 2010-09-10 | Lamberti Spa | Adjuvant compositions for herbicides |
US20110054042A1 (en) | 2009-09-01 | 2011-03-03 | Rhodia Operations | Polymer compositions |
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AU2013206347A1 (en) | 2012-06-15 | 2014-01-16 | Caltex Australia Petroleum Pty Ltd | Spray droplet modifier composition |
WO2014040119A1 (en) * | 2012-09-11 | 2014-03-20 | Vitel Australia Pty Ltd | Spray drift adjuvant formulation and method of use |
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Also Published As
Publication number | Publication date |
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KR20220004122A (ko) | 2022-01-11 |
CN113784620A (zh) | 2021-12-10 |
WO2020216872A1 (en) | 2020-10-29 |
BR112021019395A2 (pt) | 2021-12-07 |
CN113784620B (zh) | 2023-08-04 |
EP3958677A1 (en) | 2022-03-02 |
US20220192186A1 (en) | 2022-06-23 |
AU2020261248A1 (en) | 2021-11-04 |
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