EP2157852A2 - Composition d'adjuvants à base d'huile - Google Patents
Composition d'adjuvants à base d'huileInfo
- Publication number
- EP2157852A2 EP2157852A2 EP08758870A EP08758870A EP2157852A2 EP 2157852 A2 EP2157852 A2 EP 2157852A2 EP 08758870 A EP08758870 A EP 08758870A EP 08758870 A EP08758870 A EP 08758870A EP 2157852 A2 EP2157852 A2 EP 2157852A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- ammonium
- hydrogen
- compositions
- sulfate
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 134
- 239000002671 adjuvant Substances 0.000 title claims description 49
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 47
- 235000019198 oils Nutrition 0.000 claims description 47
- -1 fatty acid esters Chemical class 0.000 claims description 38
- 239000000194 fatty acid Substances 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 13
- 239000008158 vegetable oil Substances 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000000575 pesticide Substances 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 239000002480 mineral oil Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005662 Paraffin oil Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-L 2-(carboxymethyl)-2-hydroxysuccinate Chemical compound [O-]C(=O)CC(O)(C(=O)O)CC([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-L 0.000 claims description 3
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003905 agrochemical Substances 0.000 abstract description 17
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 238000009472 formulation Methods 0.000 description 29
- 239000007921 spray Substances 0.000 description 27
- 241000196324 Embryophyta Species 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 14
- 235000011130 ammonium sulphate Nutrition 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 235000019484 Rapeseed oil Nutrition 0.000 description 11
- 239000013543 active substance Substances 0.000 description 9
- 150000004702 methyl esters Chemical class 0.000 description 9
- 239000005620 Tembotrione Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 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 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004009 herbicide Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000012868 active agrochemical ingredient Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000004546 suspension concentrate Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005562 Glyphosate Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229940124532 absorption promoter Drugs 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 244000038559 crop plants Species 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 3
- 229940097068 glyphosate Drugs 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229940001447 lactate Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000004251 Ammonium lactate Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 244000141359 Malus pumila Species 0.000 description 2
- 235000011430 Malus pumila Nutrition 0.000 description 2
- 235000015103 Malus silvestris Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 239000000642 acaricide Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 229940059265 ammonium lactate Drugs 0.000 description 2
- 235000019286 ammonium lactate Nutrition 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 239000003630 growth substance Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000005645 nematicide Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003090 pesticide formulation Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQIAZOCLNBBZQK-UHFFFAOYSA-N 1-(1,2-Diphosphanylethyl)pyrrolidin-2-one Chemical compound PCC(P)N1CCCC1=O LQIAZOCLNBBZQK-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical compound OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- JQNJCQYNSLCFAC-UHFFFAOYSA-N 3-hydroxy-N-(2-methylphenyl)-4-[(2,4,5-trichlorophenyl)diazenyl]naphthalene-2-carboxamide Chemical compound CC1=CC=CC=C1NC(=O)C1=CC2=CC=CC=C2C(N=NC=2C(=CC(Cl)=C(Cl)C=2)Cl)=C1O JQNJCQYNSLCFAC-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
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- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
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- 239000003337 fertilizer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical class O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
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- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 229920000126 latex Polymers 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010496 thistle oil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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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
-
- 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
- A01N25/30—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 characterised by the surfactants
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
Definitions
- the present invention relates to novel compositions which are applicable in the field of crop protection as an adjuvant, for example in combination with agrochemical active ingredients.
- Agrochemical active substances in particular those which are applied postemergence by means of a spray and which are taken up in the plants via the leaf, are frequently used in
- the agrochemical formulations are mixed together with the tank-mix adjuvants in the spray mixture.
- These "tank-mix" adjuvants have the aim of increasing the biological activity of the agrochemically active compounds, such as insecticides, fungicides, bactericides, herbicides, growth regulators, acaricides or nematicides and / or the applicability of the agrochemically active compounds, such as insecticides, fungicides, bactericides, herbicides, growth regulators, acaricides or nematicides and / or the applicability of the agrochemically active compounds, such as insecticides, fungicides, bactericides, herbicides, growth regulators, acaricides or nematicides and / or the applicability of the agrochemically active compounds, such as insecticides, fungicides, bactericides, herbicides, growth regulators, acaricides or nematicides and / or the
- Adjuvants mean materials that are not themselves biologically active. The biological effect is e.g. improve by optimizing leaf adhesion, wetting, distribution or uptake. Some properties of the spray liquor or spray residue on the treated plant surface which can be optimized are suspensibility, emulsifiability, stability, solubility, pH, foaming, surface tension, vapor tension, plant tolerance, drift, droplet size or degree of coverage. Adjuvants may be subdivided into various chemical groups (e.g., surfactants, fatty acid esters, polymers, oils, buffers, organosilicon compounds, latex suspensions, etc.).
- chemical groups e.g., surfactants, fatty acid esters, polymers, oils, buffers, organosilicon compounds, latex suspensions, etc.
- adjuvants are of great practical importance and is described extensively in the literature (see, eg, CL Foy, DW Pritchard (Ed.), Pesticide Formulation and Adjuvant Technology, CRC Press, Ine, 1996, Boca Raton, Florida, USA; A. Knowles, Agrow Reports, Adjuvants and additives: 2006 edition, Informa UK Ltd, 2006, United Kingdom, Conference Proceedings ISAA 2004, Cape Town, South Africa).
- oils to improve the effectiveness of pesticides by improving the wetting and spreading properties of the spray residues.
- oils are mineral oils, vegetable oils and esters of these vegetable oils. It is known that vegetable oil esters improve the uptake of many pesticides into the leaf and that the very low volatility of vegetable oils increases the residual effectiveness of pesticides.
- paraffin oil formulations as a summer spray and winter spray is known in practice (eg Oleocin® from Bayer CropScience).
- US 5,580,567 compositions which contain, in addition to oil, an emulsifier system and a buffer. Advantage of these adjuvants is that the improvement of the biological effect and the ability to adjust the pH are summarized in one product.
- US 3,977,322 discloses a composition containing a mineral oil and a vegetable oil which, in admixture, enhance the effectiveness of selective herbicides.
- a synergistic herbicidal composition is described in US 4,755,207. These formulations contain a vegetable compatible oil (refined vegetable oil or high refined paraffin oil), a surfactant and hydrophobic mycobacteric spores.
- ammonium salts Another group of adjuvants is that of ammonium salts. It has already been described in the literature that the effect of various active substances can be increased by adding ammonium salts. However, these are detergent-acting salts (for example WO 95/017817) or salts with longer alkyl and / or aryl substituents, which have a permeabilizing effect or which
- Insects act (US 2,842,476).
- An increase in activity e.g. by ammonium sulfate, for example, for the herbicides glyphosate and phosphinothricin described (US 6,645,914, EP-A 0 036 106).
- ammonium sulfate as a formulation aid is described for certain active ingredients and applications (WO 92/16108), but it is there to stabilize the formulation, not to increase the effect.
- adjuvants which contain various surfactants. These surfactants, like the ammonium salts, aim to improve their uptake into the plant.
- ammonium is introduced into the formulations because the active ingredients used are used as ammonium salts, as is customary in particular in the widely used herbicide glyphosate (eg WO 07/050090, WO 05/1 17583, WO 05 / 013692, WO 06/050141, US 2003/104947, US 5,238,604, DE 197 52 552).
- a separate ammonium salt is added.
- WO 00/67573 describes adjuvants compositions for herbicides. In these, however, cationic emulsifiers are essential, while the compositions of the present invention contain anionic surfactants.
- WO 02/34047 describes a formulation aid for pesticides, in which an ammonium salt is, however, present as a solution in water, not in particulate form.
- the compositions of the present invention are anhydrous.
- Prefabricated mixtures of ammonium salts and delivery promoters such as oils and / or surfactants in a single product are beneficial to the user, e.g. with regard to dosing accuracy and user safety (no transfer and mixing necessary).
- ammonium salts in water-based adjuvant compositions is described in various publications.
- compositions which contain, in addition to water and ammonium sulfate alkylpolysaccharides.
- WO 05/046326 claims an improved uptake of nutrients into the fruit of the treated plant.
- US 5,356,861 discloses the use of a composition for increasing the effect of glyphosate.
- WO 03/092373 mentions formulations which, in addition to water and ammonium sulfate, contain an iminodipropionate as amphoteric surfactants. The aim of these formulations is to offer a complete solution as a "tank mix" for herbicides.
- oil as a receiving conveyor in combination with ammonium salt, possibly mixed with other receiving-promoting surfactants, instead of the described water-surfactant mixtures would be a logical alternative.
- adjuvant compositions either oil (s) or ammonium salt - A - included.
- One of the difficulties in developing such formulations is the form of the ammonium salt.
- the ammonium salts are in the dissolved form, resulting in a homogeneous liquid formulation.
- the solubility of the appropriate ammonium salts is less than the necessary amount of the salt.
- ammonium salt in the oil-based formulations will be in crystalline form, causing formulation problems.
- the common ammonium salts are difficult to comminute because of their hardness, and ammonium salt-containing, oil-based formulations tend to have high viscosity after comminution.
- Ammonium salts are also generally difficult to stabilize in oil-based suspension concentrates.
- the present invention thus relates to an oil-based adjuvant composition containing
- R 1, R 2, R 3 and R 4 are independently hydrogen or optionally substituted Ci-Cg-alkyl or mono- or polyunsaturated, optionally substituted C r C 8 alkylene, wherein the substituents are selected from halogen, nitro and cyano could be,
- n 1, 2, 3 or 4
- R 5 is preferably hydrogencarbonate, tetraborate, fluoride, bromide, iodide, chloride,
- oil-based composition means that the compositions according to the invention are substantially free of water, the water content being preferably less than 1.5% by weight, more preferably less than 0.7% by weight Ammonium salt of the formula (I) suspended in the compositions of the invention.
- the present invention further relates to processes for the preparation of these compositions and their use for improving the action of crop protection agents.
- the adjuvant composition of the invention can be prepared on an oil basis by
- paraffin oil 4) fatty acid esters and mixtures of different fatty acid esters
- oil-based adjuvant composition according to the invention in combination with formulations containing agrochemical active substances, is very suitable for application to plants and / or their habitat.
- oil-based adjuvant compositions according to the invention have a low viscosity and a very good stability, and in particular that no significant crystal growth of the ammonium salt was observed even after storage at changing temperature. It is also unexpected that they show significantly better biological activity than the most similar compounded adjuvant compositions. Incidentally, the oil-based adjuvant compositions according to the invention surprisingly also exceed in their activity analogous preparations which, in addition to the other components, contain either only ammonium salt or only oil. Such a synergistic effect was unpredictable due to the above-described prior art.
- the oil-based adjuvant compositions of the invention are also characterized by a number of other advantages.
- the number of necessary "tank-mix” applications is reduced because several properties to be optimized have been combined in the adjuvant compositions according to the invention
- the user will therefore need to mix his pesticides only with one instead of several mixing partners in the spray mixture
- a further advantage is that when diluting the adjuvant composition according to the invention with water, the pH of the Spray mixture is controllable by the selection of the ammonium salt in the product.
- the oil-based adjuvant composition of the invention favors the biological effectiveness of the active components of the formulations to which the adjuvant compositions are admixed so that either greater efficacy or less pesticide is required compared to conventional formulations.
- the vegetable oils contained in the adjuvant compositions of this invention are well known and commercially available.
- vegetable oils is understood as meaning, for example, oils from oil-supplying plant species such as soybean oil, rapeseed oil, corn oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, peanut oil, olive oil or castor oil, rapeseed oil, in particular soybean oil, rapeseed oil, maize germ oil or sunflower oil and their mixtures.
- the vegetable oils (triglycerides) are preferably esters of C 10 -C 22 -, preferably C 2 -C 2 o-fatty acids of glycerol.
- the Cio-C 22 -Fettklarenester of glycerol are, for example, esters of unsaturated or saturated C 2 -C 2 o-fatty acids, especially with an even number of carbon atoms, g, for example erucic acid, lauric acid, palmitic acid, and especially C] fatty acid such as stearic acid, oleic acid, linoleic acid or linolenic acid.
- Suitable mineral oils are various commercially available distillation fractions of petroleum (petroleum) in question. Mixtures of open-chain C 4 -C 3 o hydrocarbons, grokettigen hydrocarbons (naphthenes) and aromatic hydrocarbons are preferred.
- the hydrocarbons can be both linear and branched. Particular preference is given to mixtures which have an aromatic fraction of less than 8% by weight. Very particular preference is given to mixtures which have an aromatic fraction of less than 4% by weight.
- Paraffin oils linear and branched C 4 -C 3 come o-hydrocarbons. Paraffin oils are also known as base oil or white oil and are commercially available eg as Bayol® 85 (Exxon Mobil, Machelen, Belgium), Marcol® 82 (Exxon Mobil, Machelen, Belgium), BAR 0020 (RA.M.oil SpA, Naples, Italy), Pioneer 0032-20 (Hansen & Rosenthal KG, Hamburg, Germany) or eg Kristol Ml 4 (Carless, Surrey, England).
- Suitable fatty acid esters are alkyl fatty acid esters such as C 1 -C 20 -alkyl-C 20 -C 22 -fatty acid esters. Preference is given to methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters and dodecyl esters. Particularly preferred are methyl esters and ethyl esters.
- Examples of synthetic fatty acid esters are, for example, those derived from fatty acids of odd carbon number, such as Cn-C 2l fatty acid esters.
- the transesterification can be carried out by known methods, such as described in Rompp Chemie Lexikon, 9th edition, Volume 2, page 1343, Thieme Verlag, Stuttgart.
- the fatty acid esters may be present in the adjuvant compositions according to the invention in the form of commercially available esters, in particular esters such as rapeseed oil methyl ester, eg Edenor® MESU (Cognis, Germany) or the Agnique® ME series (Cognis, Germany) or in the form of commercially available oil-containing formulation additives, in particular those based on rapeseed oil methyl or ethyl esters, eg Hasten® (Victoria Chemicals, Australia), Actirob® B (Novance, France) or Stefes Mero® (Stefes, Germany).
- esters such as rapeseed oil methyl ester, eg Edenor® MESU (Cognis, Germany) or the Agnique® ME series (Cognis, Germany)
- oil-containing formulation additives in particular those based on rapeseed oil methyl or ethyl esters, eg Hasten® (Victoria Chemicals, Australia), Actirob
- Ammonium salts according to the invention are defined by formula (I)
- R 1 , R 2 , R 3 and R 4 independently of one another represent hydrogen or in each case optionally substituted CpCg-alkyl or mono- or polyunsaturated, optionally substituted C r C 8 -alkylene, where the substituents can be selected from halogen, nitro and cyano .
- R 1, R 2, R 3 and R 4 preferably each independently represent hydrogen or in each case optionally substituted C r C 4 alkyl, wherein the substituents are selected from halogen, nitro and cyano may be selected,
- R 1 , R 2 , R 3 and R 4 more preferably independently of one another are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl,
- R 1 , R 2 , R 3 and R 4 most preferably represent hydrogen
- R 1 , R 2 , R 3 and R 4 furthermore very particularly preferably mean at the same time methyl or simultaneously ethyl
- n 1, 2, 3 or 4
- n is preferably 1 or 2
- R 5 for hydrogencarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate,
- R 5 is preferably lactate, sulphate, nitrate, thiosulphate, thiocyanate, citrate, oxalate, formate, monohydrogenphosphate or dihydrogenphosphate,
- R 5 is particularly preferred for sulfate, monohydrogen phosphate or dihydrogen phosphate.
- Preferred salts are ammonium hydrogencarbonate, ammonium tetraborate, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium chloride, diammonium monohydrogenphosphate, ammonium dihydrogenphosphate, ammonium hydrogensulfate, ammonium tartrate, ammonium sulfate, ammonium nitrate, ammonium thiosulfate, ammonium thiocyanate, ammonium formate, ammonium lactate, ammonium acetate, ammonium propionate, ammonium butyrate,
- Particularly preferred salts are diammonium monohydrogenphosphate, ammonium dihydrogenphosphate, ammonium sulphate, ammonium nitrate, ammonium thiosulphate, ammonium thiocyanate, ammonium formate, ammonium lactate, ammonium citrate and ammonium oxalate.
- Particularly preferred salts are diammonium monohydrogenphosphate, ammonium dihydrogenphosphate and ammonium sulphate.
- Useful emulsifying agents are e.g. ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethoxylated arylalkylphenols, furthermore ethoxylated and propoxylated arylalkylphenols, and sulfated or phosphated arylalkylethoxylates or -ethoxy-propoxylates, wherein sorbitan derivatives, they polyethylene oxide-sorbitan fatty acid esters and sorbitan Fatty acid esters, may be mentioned as examples.
- Suitable nonionic surfactants are all substances of this type conventionally usable in agrochemical compositions.
- polyethylene oxide-polypropylene oxide block copolymers polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, furthermore polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, furthermore alkylethoxylates and Alkylaryl ethoxylates which may optionally be phosphated and optionally neutralized with bases, wherein sorbitol ethoxylates may be mentioned as examples.
- anionic surfactants are all commonly used in agrochemical agents substances of this type in question. Preference is given to alkali metal and alkaline earth metal salts of alkylsulfonic acids or alkylarylsulfonic acids.
- anionic surfactants or dispersing agents are salts of polystyrenesulfonic acids which are sparingly soluble in vegetable oil, salts of polyvinylsulfonic acids, salts of naphthalenesulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde and salts of lignosulfonic acid.
- Receiving conveyors are in this context defined by the fact that they can penetrate from the aqueous spray mixture and / or from the spray coating into the cuticle of the plant and thereby increase the material mobility (mobility) of active ingredients in the cuticle.
- the method described subsequently and in the literature can be used to determine this property.
- Suitable absorption enhancers are, for example, alkanol alkoxylates.
- Receiving promoters according to the invention are alkanol alkoxylates of the formula
- R is straight-chain or branched alkyl having 4 to 20 carbon atoms
- R ' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl or n-hexyl,
- AO is an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and
- n stands for numbers from 2 to 30.
- a preferred group of uptake promoters are alkanol alkoxylates of the formula
- R ' has the meaning given above, EO is -CH 2 -CH 2 -O- and
- A stands for numbers from 2 to 20.
- Another preferred group of uptake promoters are alkanol alkoxylates of the formula RO - (- EO-) p - (- PO-) q -R '(II-b) in which
- R ' has the abovementioned meaning, EO is -CH 2 -CH 2 -O-,
- PO is C ⁇ H ⁇ ⁇ 2 ⁇ rCH ⁇ --Ou
- p stands for numbers from 1 to 10 and q stands for numbers from 1 to 10.
- alkanol alkoxylates of the formula RO - (- PO-) r - (EO-) s -R '(II-c) in which
- R ' has the abovementioned meaning, EO is -CH 2 -CH 2 -O-,
- PO is CH-CH-O ;
- CH 3 r stands for numbers from 1 to 10
- s stands for numbers from 1 to 10.
- absorption promoters are alkanol alkoxylates of the formula
- EO is CH 2 -CH 2 -O-
- BO is - CH 1 -CHj-? CH-O
- v stands for numbers from 1 to 10
- x stands for numbers from 1 to 10.
- absorption promoters are alkanol alkoxylates of the formula
- BO represents - CH 1 CH 2 CH 2 TCH-O
- EO is CH 2 -CH 2 -O-
- y stands for numbers from 1 to 10
- z stands for numbers from 1 to 10.
- absorption promoters are alkanol alkoxylates of the formula
- u stands for numbers from 6 to 17.
- R is preferably butyl, isobutyl, n-pentyl, i-pentyl, neopentyl, n-hexyl, i-hexyl, n-octyl, i-octyl, 2-ethylhexyl, nonyl, i-nonyl, decyl, n Dodecyl, i-dodecyl, lauryl, myristyl, i-tridecyl, trimethylnonyl, palmityl, stearyl or eicosyl.
- ethoxylated Guerbet alcohols of the formula (II-a-1) may be mentioned:
- R is a Ci 6 -C
- R ' is n-butyl, i-butyl or t-butyl
- b stands for numbers from 4 to 10.
- alkanol alkoxylate of the formula (II-c) is 2-ethyl-hexyl alkoxylate of the formula
- EO stands for -CH 2 -CH 2 -O-, -CH- CH-O stands and
- the numbers 8 and 6 represent average values called.
- EO is CH 2 -CH 2 -O-
- BO is - CH-CHj-TCH-O
- the numbers 10, 6 and 2 represent average values called.
- Particularly preferred alkanol alkoxylates of the formula (II-f) are compounds of this formula in which
- u stands for the average 8.4.
- the alkanol alkoxylates are generally defined by the above formulas. These substances are mixtures of substances of the specified type with different chain lengths. For the indices, therefore, average values are calculated, which can also differ from whole numbers.
- the alkanol alkoxylates of the formulas given are known and are partly available commercially or can be prepared by known methods (cf., WO 98-35553, WO 00-35278 and EP-A 0 681 865).
- Suitable foam-inhibiting substances are all substances customarily usable for this purpose in agrochemical compositions.
- Preferred are silicone oils and magnesium stearate.
- Suitable preservatives are all substances customarily usable for this purpose in agrochemical compositions of this type. Examples which may be mentioned are Preventol® (Bayer AG) and Proxel®.
- antioxidants are all commonly used for this purpose in agrochemical agents substances into consideration. Preference is given to 2,6-di-tert-butyl-4-methylphenol.
- Suitable dyes are all substances customarily usable for this purpose in agrochemical compositions. Examples include titanium dioxide, carbon black, zinc oxide and blue pigments as well as permanent red FGR.
- Suitable thickeners are all substances which can usually be used for this purpose in agrochemical compositions and which act as thickeners. Preference is given to inorganic particles, such as carbonates, silicates and oxides, and also organic substances, such as urea-formaldehyde condensates. Examples include kaolin, rutile, silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates such as bentonites, attapulgites or montmorillites, and also talc.
- the present invention relates to an oil-based adjuvant composition containing
- ammonium salt selected from ammonium sulfate and Ammoniumdihydrogensul fat
- compositions according to the invention can be varied within a relatively wide range in the compositions according to the invention.
- the production of the oil-based adjuvant compositions according to the invention takes place in such a way that the components are mixed together in the respectively desired ratios.
- the order in which the ingredients are mixed together is arbitrary. Conveniently, one uses the solid components in a finely ground state. However, it is also possible first to subject the suspension formed after mixing the constituents to a coarse and then to a fine grinding so that the mean particle size is less than 20 ⁇ m. Preference is given to suspension concentrates in which the solid particles have an average particle size of between 1 and 10 ⁇ m.
- the temperatures can be varied in carrying out the method according to the invention in a certain range. It generally works at temperatures between 10 0 C and 60 0 C, preferably between 15 ° C and 40 0 C.
- customary mixing and grinding devices which are used for the production of agrochemical formulations are suitable.
- oil-based adjuvant compositions according to the invention are formulations which remain stable even after prolonged storage at elevated temperatures or in the cold, since no crystal growth is observed. They can be converted by dilution with water into homogeneous spray liquids.
- the adjuvant compositions of the present invention may be used in combination with various pesticidal formulations. Preference is given to pesticide formulations which contain one or more active substances from the groups of insecticides, fungicides, bactericides, herbicides, growth regulators, acaricides or nematicides. In addition, they can be applied in combination with fertilizer and / or other nutrients.
- the optimal effect of the application may be influenced by the type of plant being treated, disease, spray equipment, shot volume, pressure, droplet size, mixing partner, environmental factors and other factors. Accordingly, it is important to observe the spray coating formed by the treatment and, if necessary, to adjust the use concentration of the adjuvant composition.
- the weight ratio of agrochemical active ingredient to adjuvant composition according to the invention is generally in the range 1: 10000 to 100: 1, in particular 1: 1000 to 10: 1, depending on the activity of the respective agrochemical active ingredient.
- the concentration of agrochemical active ingredient is generally at 10 "6 to 10 wt .-%, preferably at 10 " 5 to 4 wt .-% in the applied agent, eg the spray mixture, at an application rate of 1 to 5000 l / ha, preferably 50 to 1000 l / ha.
- the concentration of adjuvant composition according to the invention is generally from 0.005 to 5% by weight, preferably from 0.05 to 3% by weight, in the applied agent, for example the spray mixture, at an application rate of from 1 to 5000 l / ha. preferably 50 to 1000 l / ha.
- half of the syringe tank is filled with water and stirred.
- the various products are added, the following series being followed: First, the solid formulations are stirred, then the suspension concentrates and the adjuvant composition according to the invention, and finally the homogeneous liquid formulations.
- the spray tank is filled with water and homogenized again.
- agrochemical active substances can be applied in a particularly advantageous manner to plants and / or their habitat.
- plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
- Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
- Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
- the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
- the contained agrochemical active ingredients develop a better biological effectiveness than when applied in the form of the corresponding conventional formulations.
- compositions according to the invention defined by their trade names are available from the following suppliers:
- TW 6 hours at -15 ° C, then 6 hours at +30 0 C
- Sediment volume volume of the sediment phase in relation to the total volume of the sample.
- the viscosity was measured at a shear rate of 7.5 (l / s) on a rheometer of the type DSR 301 from Anton Paar. Table 4
- Sediment volume volume of the sediment phase in relation to the total volume of the sample.
- the viscosity was measured at a shear rate of 7.5 (l / s) on a rheometer of the type DSR 301 from Anton Paar.
- / Sediment volume volume of the sediment phase in relation to the total volume of the sample.
- Sheets were used, which were cut in the fully developed state of apple trees of the variety Golden Delicious. The isolation of the cuticles took place in such a way that
- the cuticles were placed with tweezers in the middle of the silicone grease-coated edges of the diffusion cells and sealed with a likewise greased ring.
- the arrangement was chosen so that the morphological outside of the cuticles was directed outward, ie towards the air, while the original inner side faced the interior of the diffusion cell.
- the diffusion cells were filled with water or with a mixture of water and solvent.
- Rapeseed oil methyl ester was used as RME EW 500 (50% rapeseed oil methyl ester, 0.5% Pluronic® PE 10500 (BASF), balance water).
- Rapeseed oil methyl ester was used as RME EW 500 (50% rapeseed oil methyl ester, 0.5% Pluronic® PE 10500 (BASF), balance water).
- Spray mixture D (Invention according to)
- Spray mixture F ( " according to the invention)
- CEPAC C water was used in the spray mixtures.
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Abstract
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08758870A EP2157852A2 (fr) | 2007-06-12 | 2008-05-30 | Composition d'adjuvants à base d'huile |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07110022A EP2002719A1 (fr) | 2007-06-12 | 2007-06-12 | Composition d'adjuvants à base d'huile |
| PCT/EP2008/004292 WO2008151725A1 (fr) | 2007-06-12 | 2008-05-30 | Nouvelle composition d'adjuvant à base d'huile |
| EP08758870A EP2157852A2 (fr) | 2007-06-12 | 2008-05-30 | Composition d'adjuvants à base d'huile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2157852A2 true EP2157852A2 (fr) | 2010-03-03 |
Family
ID=38617524
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07110022A Withdrawn EP2002719A1 (fr) | 2007-06-12 | 2007-06-12 | Composition d'adjuvants à base d'huile |
| EP08758870A Withdrawn EP2157852A2 (fr) | 2007-06-12 | 2008-05-30 | Composition d'adjuvants à base d'huile |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| EP07110022A Withdrawn EP2002719A1 (fr) | 2007-06-12 | 2007-06-12 | Composition d'adjuvants à base d'huile |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US20100179228A1 (fr) |
| EP (2) | EP2002719A1 (fr) |
| JP (1) | JP2010530365A (fr) |
| KR (1) | KR20100046110A (fr) |
| CN (1) | CN101677528A (fr) |
| AR (1) | AR066934A1 (fr) |
| AU (1) | AU2008261348A1 (fr) |
| BR (1) | BRPI0813810A2 (fr) |
| CA (1) | CA2694028A1 (fr) |
| CL (1) | CL2008001606A1 (fr) |
| CO (1) | CO6241135A2 (fr) |
| MX (1) | MX2009013536A (fr) |
| TW (1) | TW200906296A (fr) |
| WO (1) | WO2008151725A1 (fr) |
| ZA (1) | ZA200908127B (fr) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0907003D0 (en) * | 2009-04-23 | 2009-06-03 | Syngenta Ltd | Formulation |
| US8975214B2 (en) | 2010-02-23 | 2015-03-10 | Innovative Chemical Services Pty Ltd | Emulsion adjuvant for herbicides |
| US20110218104A1 (en) * | 2010-03-03 | 2011-09-08 | Auburn University | Biodiesel Solvents in Pesticide Compositions |
| WO2011117891A2 (fr) * | 2010-03-25 | 2011-09-29 | Indian Oil Corporation Ltd. | Composition d'huile de transport pour pulvérisation de fongicides dans des plantations d'hévéas et autres |
| US20110306643A1 (en) * | 2010-04-23 | 2011-12-15 | Bayer Cropscience Ag | Triglyceride-containing dormancy sprays |
| EP2446743B1 (fr) * | 2010-10-26 | 2014-06-04 | Cognis IP Management GmbH | Compositions biocides comprenant des esters d'alcools éthoxylés |
| CN102391781B (zh) * | 2011-07-14 | 2013-08-07 | 欧德力(厦门)汽车环保科技有限公司 | 电瓶桩头保护剂及其制备方法 |
| CA2992119C (fr) | 2015-07-14 | 2023-08-29 | Rhodia Operations | Compositions d'adjuvant agricole d'emulsions d'huile/tensioactif/sel et procedes d'utilisation |
| GB201714024D0 (en) * | 2017-09-01 | 2017-10-18 | Syngenta Participations Ag | Adjuvants |
| AU2019250617B2 (en) * | 2018-04-13 | 2025-01-02 | Bayer Aktiengesellschaft | Formulation of insecticidal mixtures comprising propylene carbonate |
| EP4275492A1 (fr) | 2019-10-10 | 2023-11-15 | Bayer Aktiengesellschaft | Formulation d'insecticides comprenant du carbonate de propylène |
| TWI861248B (zh) * | 2019-10-10 | 2024-11-11 | 德商拜耳廠股份有限公司 | 含二醇醚溶劑之殺蟲劑調配物 |
| TWI867064B (zh) * | 2019-10-10 | 2024-12-21 | 德商拜耳廠股份有限公司 | 包含乙二醇醚溶劑之殺昆蟲混合物調配物 |
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| DE19752552A1 (de) * | 1997-11-27 | 1999-06-02 | Hoechst Schering Agrevo Gmbh | Tensidsysteme für flüssige wässrige Zubereitungen |
| DE19857963A1 (de) * | 1998-12-16 | 2000-06-21 | Bayer Ag | Agrochemische Formulierungen |
| AUPQ017599A0 (en) * | 1999-05-05 | 1999-05-27 | Victorian Chemicals International Pty Ltd | Adjuvant composition for chemicals used in agriculture |
| CN1398159A (zh) * | 2000-02-11 | 2003-02-19 | 瓦伦特美国公司 | 二苯醚诱导植物体系统性抗性 |
| CA2324677A1 (fr) * | 2000-10-26 | 2002-04-26 | James F. Stewart | Additif agrochimique |
| US6423667B1 (en) * | 2001-05-15 | 2002-07-23 | Honeywell International Inc. | Ammonium sulfate suspensions in oils |
| DE10129855A1 (de) * | 2001-06-21 | 2003-01-02 | Bayer Ag | Suspensionskonzentrate auf Ölbasis |
| US6689720B2 (en) * | 2001-11-14 | 2004-02-10 | Ndsu-Research Foundation | High-pH oil based adjuvant blend for enhancing efficacy of pesticides |
| US6645914B1 (en) * | 2002-05-01 | 2003-11-11 | Ndsu-Research Foundation | Surfactant-ammonium sulfate adjuvant composition for enhancing efficacy of herbicides |
| WO2003101197A1 (fr) * | 2002-05-31 | 2003-12-11 | Cjb Industries, Inc. | Additif pour pesticides |
| AU2003281148A1 (en) * | 2002-07-12 | 2004-02-02 | Bayer Cropscience Ag | Liquid adjuvants |
| US6984662B2 (en) * | 2003-11-03 | 2006-01-10 | The Hartz Mountain Corporation | High concentration topical insecticide containing insect growth regulator |
| US7132448B2 (en) * | 2002-09-12 | 2006-11-07 | The Hartz Mountain Corporation | High concentration topical insecticide containing insect growth regulator |
| GB0318448D0 (en) * | 2003-08-06 | 2003-09-10 | Syngenta Ltd | Formulation |
| DE102004011007A1 (de) * | 2004-03-06 | 2005-09-22 | Bayer Cropscience Ag | Suspensionskonzentrate auf Ölbasis |
| DE102004026937A1 (de) * | 2004-06-01 | 2005-12-22 | Bayer Cropscience Gmbh | Konzentrierte wäßrige Formulierungen für den Pflanzenschutz |
| US7651977B2 (en) * | 2004-10-28 | 2010-01-26 | Valent U.S.A. Corporation | Herbicidal compositions |
| DE102005018262A1 (de) * | 2005-04-20 | 2006-10-26 | Bayer Cropscience Ag | Suspensionskonzentrate auf Ölbasis |
| EP1728430A1 (fr) * | 2005-06-04 | 2006-12-06 | Bayer CropScience GmbH | Agents herbicides |
| WO2007050090A1 (fr) * | 2005-10-28 | 2007-05-03 | Valent U.S.A. Corporation | Compositions herbicides |
| EP2092822A1 (fr) * | 2008-02-25 | 2009-08-26 | Bayer CropScience AG | Suspensions concentrées à base d'huile |
| US20120122696A1 (en) * | 2010-05-27 | 2012-05-17 | Bayer Cropscience Ag | Use of oil based suspension concentrates for reducing drift during spray application |
-
2007
- 2007-06-12 EP EP07110022A patent/EP2002719A1/fr not_active Withdrawn
-
2008
- 2008-05-30 WO PCT/EP2008/004292 patent/WO2008151725A1/fr not_active Ceased
- 2008-05-30 CN CN200880019796A patent/CN101677528A/zh active Pending
- 2008-05-30 JP JP2010511518A patent/JP2010530365A/ja active Pending
- 2008-05-30 KR KR1020097027333A patent/KR20100046110A/ko not_active Withdrawn
- 2008-05-30 MX MX2009013536A patent/MX2009013536A/es unknown
- 2008-05-30 CA CA2694028A patent/CA2694028A1/fr not_active Abandoned
- 2008-05-30 US US12/664,284 patent/US20100179228A1/en not_active Abandoned
- 2008-05-30 AU AU2008261348A patent/AU2008261348A1/en not_active Abandoned
- 2008-05-30 EP EP08758870A patent/EP2157852A2/fr not_active Withdrawn
- 2008-05-30 BR BRPI0813810-9A2A patent/BRPI0813810A2/pt not_active Application Discontinuation
- 2008-06-02 CL CL2008001606A patent/CL2008001606A1/es unknown
- 2008-06-09 AR ARP080102456A patent/AR066934A1/es not_active Application Discontinuation
- 2008-06-11 TW TW097121623A patent/TW200906296A/zh unknown
-
2009
- 2009-11-18 ZA ZA2009/08127A patent/ZA200908127B/en unknown
- 2009-12-11 CO CO09141628A patent/CO6241135A2/es not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2008151725A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100046110A (ko) | 2010-05-06 |
| AU2008261348A1 (en) | 2008-12-18 |
| TW200906296A (en) | 2009-02-16 |
| JP2010530365A (ja) | 2010-09-09 |
| MX2009013536A (es) | 2010-01-26 |
| CL2008001606A1 (es) | 2008-12-19 |
| US20100179228A1 (en) | 2010-07-15 |
| WO2008151725A1 (fr) | 2008-12-18 |
| CA2694028A1 (fr) | 2008-12-18 |
| BRPI0813810A2 (pt) | 2015-01-06 |
| CO6241135A2 (es) | 2011-01-20 |
| EP2002719A1 (fr) | 2008-12-17 |
| AR066934A1 (es) | 2009-09-23 |
| CN101677528A (zh) | 2010-03-24 |
| WO2008151725A8 (fr) | 2010-04-01 |
| ZA200908127B (en) | 2011-06-29 |
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