WO2008061721A2 - Novel agrochemical formulations containing microcapsules - Google Patents
Novel agrochemical formulations containing microcapsules Download PDFInfo
- Publication number
- WO2008061721A2 WO2008061721A2 PCT/EP2007/010073 EP2007010073W WO2008061721A2 WO 2008061721 A2 WO2008061721 A2 WO 2008061721A2 EP 2007010073 W EP2007010073 W EP 2007010073W WO 2008061721 A2 WO2008061721 A2 WO 2008061721A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microcapsules
- styrene acrylic
- fluroxypyr
- acrylic polymer
- active ingredient
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 238000009472 formulation Methods 0.000 title claims abstract description 70
- 239000003094 microcapsule Substances 0.000 title claims abstract description 52
- 239000003905 agrochemical Substances 0.000 title claims abstract description 38
- 239000005558 Fluroxypyr Substances 0.000 claims abstract description 47
- MEFQWPUMEMWTJP-UHFFFAOYSA-N fluroxypyr Chemical compound NC1=C(Cl)C(F)=NC(OCC(O)=O)=C1Cl MEFQWPUMEMWTJP-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004480 active ingredient Substances 0.000 claims abstract description 32
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005944 Chlorpyrifos Substances 0.000 claims abstract description 27
- 229940100389 Sulfonylurea Drugs 0.000 claims abstract description 26
- 239000008187 granular material Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000005507 Diflufenican Substances 0.000 claims abstract description 8
- WYEHFWKAOXOVJD-UHFFFAOYSA-N diflufenican Chemical compound FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 WYEHFWKAOXOVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004490 capsule suspension Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 35
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 claims description 18
- -1 aromatic isocyanate Chemical class 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 239000004546 suspension concentrate Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000005538 encapsulation Methods 0.000 claims description 6
- 239000013020 final formulation Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000005586 Nicosulfuron Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- RBSXHDIPCIWOMG-UHFFFAOYSA-N 1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-yl)sulfonylurea Chemical compound CCS(=O)(=O)C=1N=C2C=CC=CN2C=1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 RBSXHDIPCIWOMG-UHFFFAOYSA-N 0.000 claims description 3
- MBFHUWCOCCICOK-UHFFFAOYSA-N 4-iodo-2-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoylsulfamoyl]benzoic acid Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=C(I)C=2)C(O)=O)=N1 MBFHUWCOCCICOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003666 Amidosulfuron Substances 0.000 claims description 3
- CTTHWASMBLQOFR-UHFFFAOYSA-N Amidosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)N(C)S(C)(=O)=O)=N1 CTTHWASMBLQOFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005469 Azimsulfuron Substances 0.000 claims description 3
- 239000005496 Chlorsulfuron Substances 0.000 claims description 3
- WMLPCIHUFDKWJU-UHFFFAOYSA-N Cinosulfuron Chemical compound COCCOC1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC)=NC(OC)=N1 WMLPCIHUFDKWJU-UHFFFAOYSA-N 0.000 claims description 3
- UWVKRNOCDUPIDM-UHFFFAOYSA-N Ethoxysulfuron Chemical compound CCOC1=CC=CC=C1OS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 UWVKRNOCDUPIDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005514 Flazasulfuron Substances 0.000 claims description 3
- HWATZEJQIXKWQS-UHFFFAOYSA-N Flazasulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(F)(F)F)=N1 HWATZEJQIXKWQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005560 Foramsulfuron Substances 0.000 claims description 3
- LXKOADMMGWXPJQ-UHFFFAOYSA-N Halosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=C(Cl)C=2C(O)=O)C)=N1 LXKOADMMGWXPJQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005567 Imazosulfuron Substances 0.000 claims description 3
- NAGRVUXEKKZNHT-UHFFFAOYSA-N Imazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N3C=CC=CC3=NC=2Cl)=N1 NAGRVUXEKKZNHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005568 Iodosulfuron Substances 0.000 claims description 3
- 239000005589 Oxasulfuron Substances 0.000 claims description 3
- GPGLBXMQFQQXDV-UHFFFAOYSA-N Primisulfuron Chemical compound OC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 GPGLBXMQFQQXDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005604 Prosulfuron Substances 0.000 claims description 3
- LTUNNEGNEKBSEH-UHFFFAOYSA-N Prosulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)CCC(F)(F)F)=N1 LTUNNEGNEKBSEH-UHFFFAOYSA-N 0.000 claims description 3
- VXMNDQDDWDDKOQ-UHFFFAOYSA-N Pyrazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C(O)=O)C)=N1 VXMNDQDDWDDKOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005616 Rimsulfuron Substances 0.000 claims description 3
- 239000005619 Sulfosulfuron Substances 0.000 claims description 3
- 239000005626 Tribenuron Substances 0.000 claims description 3
- 239000005629 Tritosulfuron Substances 0.000 claims description 3
- MAHPNPYYQAIOJN-UHFFFAOYSA-N azimsulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C2=NN(C)N=N2)C)=N1 MAHPNPYYQAIOJN-UHFFFAOYSA-N 0.000 claims description 3
- PPWBRCCBKOWDNB-UHFFFAOYSA-N bensulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)CC=2C(=CC=CC=2)C(O)=O)=N1 PPWBRCCBKOWDNB-UHFFFAOYSA-N 0.000 claims description 3
- RIUXZHMCCFLRBI-UHFFFAOYSA-N chlorimuron Chemical compound COC1=CC(Cl)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 RIUXZHMCCFLRBI-UHFFFAOYSA-N 0.000 claims description 3
- VJYIFXVZLXQVHO-UHFFFAOYSA-N chlorsulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)Cl)=N1 VJYIFXVZLXQVHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- PXDNXJSDGQBLKS-UHFFFAOYSA-N foramsulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=C(NC=O)C=2)C(=O)N(C)C)=N1 PXDNXJSDGQBLKS-UHFFFAOYSA-N 0.000 claims description 3
- AIMMSOZBPYFASU-UHFFFAOYSA-N n-(4,6-dimethoxypyrimidin-2-yl)-n'-[3-(2,2,2-trifluoroethoxy)pyridin-1-ium-2-yl]sulfonylcarbamimidate Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)OCC(F)(F)F)=N1 AIMMSOZBPYFASU-UHFFFAOYSA-N 0.000 claims description 3
- IOXAXYHXMLCCJJ-UHFFFAOYSA-N oxetan-3-yl 2-[(4,6-dimethylpyrimidin-2-yl)carbamoylsulfamoyl]benzoate Chemical compound CC1=CC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(=O)OC2COC2)=N1 IOXAXYHXMLCCJJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FZMKKCQHDROFNI-UHFFFAOYSA-N sulfometuron Chemical compound CC1=CC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 FZMKKCQHDROFNI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 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 claims description 3
- 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 claims description 3
- MAYMYMXYWIVVOK-UHFFFAOYSA-N 2-[(4,6-dimethoxypyrimidin-2-yl)carbamoylsulfamoyl]-4-(methanesulfonamidomethyl)benzoic acid Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=C(CNS(C)(=O)=O)C=2)C(O)=O)=N1 MAYMYMXYWIVVOK-UHFFFAOYSA-N 0.000 claims description 2
- OFSLKOLYLQSJPB-UHFFFAOYSA-N Cyclosulfamuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)NC=2C(=CC=CC=2)C(=O)C2CC2)=N1 OFSLKOLYLQSJPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005577 Mesosulfuron Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920002396 Polyurea Polymers 0.000 claims 8
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical class N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims 4
- 241000238631 Hexapoda Species 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- 230000001804 emulsifying effect Effects 0.000 claims 2
- 230000004071 biological effect Effects 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000002775 capsule Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000005584 Metsulfuron-methyl Substances 0.000 description 5
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- UWHURBUBIHUHSU-UHFFFAOYSA-N 2-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoylsulfamoyl]benzoic acid Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 UWHURBUBIHUHSU-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229940086542 triethylamine Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004562 water dispersible granule Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 description 1
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010068516 Encapsulation reaction Diseases 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- OQZCSNDVOWYALR-UHFFFAOYSA-N flurochloridone Chemical compound FC(F)(F)C1=CC=CC(N2C(C(Cl)C(CCl)C2)=O)=C1 OQZCSNDVOWYALR-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000005910 lambda-Cyhalothrin Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 1
- HCJTYESURSHXNB-UHFFFAOYSA-N propynamide Chemical class NC(=O)C#C HCJTYESURSHXNB-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- 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
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
Definitions
- microencapsulation is a technique that offers a number of advantages in front of other formulation techniques in the field of Agrochemistry.
- Modern agricultural practice requires controlling the application of biological active components to the target. This allows: to increase compounds stability over extended periods of time, to reduce environmental hazards, to decrease acute toxicity, and to deal with incompatibility between ingredients.
- Fluids are used as functional inerts in high technology formulations, e.g. allowing encapsulation of solid active ingredients and adjusting the diffusion rate of the active substance.
- CS microcapsule suspension
- Chlorpyrifos CS 1 Lambdacyhalothrin CS, Fluorochloridone CS, and Methylparathion CS When dryied, they may form water dispersable granules containing microcapsules.
- a typical method of CS manufacture by interfacial polymerisation is to dissolve the active ingredient, monomers or prepolymers in a fluid (oil phase).
- the latter is dispersed into the water phase, which contains emulsifiers, protective colloids (and eventually additional prepolymers).
- the capsule wall around the oil droplet is formed by polymerisation at the interface of water and oil in the presence of a catalyst or by heat. Many wall-forming materials are available for the encapsulation of liquid or solid active ingredients. The release rate of the latter can be adjusted by selecting the optimum
- the scope of this invention is to facilitate the production of agrochemical formulations in the form of capsule suspension (CS) and/or ZC and/or WG in a unified production process. Also is object of the invention to potect the microcapsules, CS, ZC and WG formulations of active ingredients never encapsulated before in these type of formulations and also the process characterized in that selected coformulants, wall forming materials are both able to reach a CS formulation and, at the desire of the producer, to proceed further without essential changes to spray dry this CS to form a WG of microcapsules.
- sulfonylureas plus other actives microencapsulated are milled to form a suspension concentrate (SC), and then the CS suspension is added to the SC.
- SC suspension concentrate
- the SC contain other sulfonylurea- compatible agrochemicals and optionally the microcapsules contain a mixture of several acives compatible in between them.
- One of the novelty aspects of this invention is the ability to have an "oil phase" (inside microcapsules) where the only requisite is that in such phase the oil soluble materials are compatible, and a "water phase” where the same requisite applies, but it is not necessary that the oil soluble actives and the water soluble acives are compatible in between them.
- the present invention has its more powerful sense when the active ingredients in and out- of the microcapsules- are incompatible in the broad sense, namely, that the activity is reduced because any reason including chemical reaction in between incompatible materials, adsorption, crystallization induction, etc.
- Chlorpyrifos microcapsules in the form of water dispersable granules are known from a number of patents of Dow and Monsanto. However, the processes so far disclosed differ in the process of the present invention.
- the use of our wall foming materials lead to a taylor made release rate, easier to predict and control than when conventional microencapsulating techniques are used.
- Fluroxypyr on the other side has neve been described in microencapsulated form, at least in a enable disclosure, and lesser having the extraordinary formulation poperties described herein regarding also particle size, and long term stability, and w.hen in WG (CS) formulation, the high dispersibility and suspensibility properties
- the preferred materials are those having a low melting point as one of the materials to microencapsulate, at least one of the actives (if chosen to be more than one) to be inside the microcapsules. Outside of the microcapsules, optionally it is used a sulfonylurea or any suitable agrochemical.
- a low melting point as one of the materials to microencapsulate
- the actives if chosen to be more than one
- a sulfonylurea or any suitable agrochemical any suitable agrochemical.
- Example 1 A typical composition to microencapsulate would be, for fluroxypyr, as follows (in w/w %):
- the surfactant system (including dispersants and wettings) has two properties: 1) be able to be stable at a wide range of pHs, to be able to be used for encapsulation of different actives and 2) have a cloud point over the melting point of the desired agrochemical to encapsulate, concomitantly, preventing phase inversion during the process.
- Metasperse 500 series we have not found any other better dispersant for the purposes of both being able to have a good CS suspension, to spray dry it and have a good WG formulation or to mix with an SC to have a good ZC formulation. Further we have found incredibly that the properties of Atlox Metasperse 500L in order to prevent Ostwald ripening forces and agglomeration processes is valid for all formulations of the type CS, ZC and WG (of capsules), making our desired target of an "unified" process for different formulation times a reality.
- the type of compounds preferred are styrene acrylic polymers, but more preferentially, and with evident better performance anionically substituted styrene acrylic polymers, being this anionic substituents being chosen from a wide range, preferably, but not necessarily from sulphonates and phosphates.
- both mentioned phases are mixed (emulsionated) at a suitable speed of an ultraturrax type mixer (e.g., 2000 rpm) for a short time (e.g., 10 minutes), adding the catalizator short after the emulsification step begins (e.g., 1 to 3 minutes) till obtaining a particle size of about 1 to 30 ⁇ m, being obvious that other sizes may be selected. Then a cooking process is initiated, for some hours (typically 2 h), and the capsules are hardened.
- an ultraturrax type mixer e.g. 2000 rpm
- a short time e.g. 10 minutes
- adding the catalizator short after the emulsification step begins e.g., 1 to 3 minutes
- a cooking process is initiated, for some hours (typically 2 h), and the capsules are hardened.
- a cooling and filtering step follows to obain a agriculturally suitable CS formulation of fluroxypyr (or of any other agrochemical that is solid at room temperature and with a low melting point -below about 11O 0 C, as far as the surfactant does not reach the cloud point).
- Both the fluroxypyr CS and the methsulfuron-methyl SC may be mixed in the desired proportion to obtain the desired final formulation of acive ingredients, having the metsulfuron-methyl SC the necessary coformulants for a perfect formulation stability.
- the mixture must be adjusted for the purposes of spray drying.
- the content of the styrene acrylic polymer may vary in between 1 to 45% in w/w in the final formulation.
- Metasperse 500 Series or any similar dispersant type of the same chemical class (modified styrene acrylic polymer or anionically modified styrene acrylic polymer, more preferably of the second class) in an amount of 2 to 20 % in w/w related to total weight of liquid to spray and from 0.1 to 15 % of any sulfosuccynate available in catalogs for the agrochemical industry (e.g., Clariant, Uniquema, Cognis, etc) or similar type of chemical.
- Metasperse 500 Series or any similar dispersant type of the same chemical class (modified styrene acrylic polymer or anionically modified styrene acrylic polymer, more preferably of the second class) in an amount of 2 to 20 % in w/w related to total weight of liquid to spray and from 0.1 to 15 % of any sulfosuccynate available in catalogs for the agrochemical industry (e.g., Clariant, Uniquema,
- the product is spray dryed at a temperature of the product slightly below the melting point (e.g., for Chlopyrifos 35°C, for the example above 40-45 0 C) and a temperature of the air of 70-75 %.
- the WG consisting of microcapsules is deemed to be enough dried when the humidity is below 0.5%.
- One of the main targets of the combination of microencapsulated material mixed with unencapsulated materials is to achieve a longer stability of the most labile compound.
- Test Item ID Number 1 FXY- GLASS 1 ' PLASTIC 2 ' GLASS 3 ' PLASTIC 4 ' MSF 0604 54 ⁇ 2 0 C, 54 ⁇ 2 0 C, 0 ⁇ 2 0 C, 0 ⁇ 2 0 C, after storage after storage after storage after storage after storage
- Fluroxypyr to certain extent, also degradates: the fact that in cold fluroxypyr is reasonably well conserved means that in a non- microencapsulated flurosypyr WDG (with a sulfonylurea) the reaction of degradation takes place on the finished product, and not during the production of the WG.
- One of the most surpresive aspects of the invention is the inclusion as a best choice dispersant the anionically modified styrene acrylic polymers.
- This class of surfacgants shows to: 1- Provide a very good dispersion of the microcapsules 2- Provide a perfect compatibility with an SC, where the same polymer can be used as a dispersant.
- Chlorpyrifos 750 g/kg WG consists of two components, a capsule suspension and an adjustment mixture.
- the capsule suspension works as base for different formulations depending on the adjustment, like 240 g/L CS, 400 g/L CS and 750 g/kg WG.
- the target is to achieve both a "ready to use" CS formulation, and for the costumers interested in having a WG (CS), to be able to use the same produced CS and proceed to spray dry.
- CS WG
- two hundred capsule suspensions have been done during the development, being adjusted with hundred eighty different adjustment mixtures.
- the catalyst may be for procedural reasons to be dibutyltinlaurate, but the best control of the reaction is achieved by an emulsified catalyst (not soluble in water, but emulsified in it, a concept completely new).
- Some details to handle this unique type of catalyst in the microencapsulation field is that The components of the Catalyst are mixed together using an ultrasonic bath or Ultrathurrax to homogenize in no special order at room temperature. Care has to be taken that the catalyst will separate within 24 hours and therefore should be homogenized prior to addition.of the catalyst was prepared by mixing the components for 100 ml_ (water, Symperonic PE/L64, Triethylamine) by simple shaking in a bottle. In fact the catalyst in chemical sense is the triethylamine, but the real "catalyst" in the practice is this emulsion (comparable to platinum alone and platinum in carbon support).
- Geropon DOS/PG 20.60 3.49 Further is we want to spray dry this CS formulation of chlorpyrifos, we proceed as follows in the spray drier:
- sulfonylureas that may be used in the present invention are:
- fluroxypyr for combination with sulfonylurea or not
- fluroxypyr for combination with sulfonylurea or not
- the sulfonylureas for the purpose of protection against degradation may be well encapsulated according process using anionic substituted acrylic styrene polymers as dispersing agents, and optionally, encapsulated in such way that the encapsulation reaction takes place thanks to an emulsified catalyst (a polyamine). They may be as well microencapsulated according the European Patent Application EP 06006748, of the same inventors and applied by GAT Formulation GmbH (reference incorporated for all this patent document in its totality for the purpose of microcapsules containing acetylene carbamide derivatives in the wall) and then create the WG.
- cofomulants for the creation of the CS 1 SC, ZC and WG formulations are in no way limited to the compounds mentioned in the examples: what is important is that the chemical class of chemicals remains as closer as possible.
- isocyanates as wall forming materials
- polyamines or alkyltin fatty esthers as catalysts
- sulfosuccinate addition before spray drying etc.
- the wall forming materials may be composed of mixures of isocyanates or mixtures of aromatic isocyanate(s), aliphatic isocyanate(s) and glicoluril derivatives having the four hydroxylgroups substituting the four nitrogen atoms of the five membered cycle replaced by a alkyloxyalkylen group, where alkylene has the meaning of methylen, ethylen, isopropylen, and alkyl the meaning methyl, ethyl, isopropyl.
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Polymers & Plastics (AREA)
- Pest Control & Pesticides (AREA)
- Medicinal Chemistry (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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AU2007323316A AU2007323316B2 (en) | 2006-11-23 | 2007-11-21 | Novel agrochemical formulations containing microcapsules |
BRPI0719120A BRPI0719120A8 (en) | 2006-11-23 | 2007-11-21 | NEW AGROCHEMICAL FORMULATIONS CONTAINING MICROCAPSULES |
MX2009005419A MX2009005419A (en) | 2006-11-23 | 2007-11-21 | Novel agrochemical formulations containing microcapsules. |
US12/312,644 US8263530B2 (en) | 2006-11-23 | 2007-11-21 | Agrochemical formulations containing microcapsules |
CA2669478A CA2669478C (en) | 2006-11-23 | 2007-11-21 | Novel agrochemical formulations containing microcapsules |
CN200780043491.6A CN101583269B (en) | 2006-11-23 | 2007-11-21 | Novel pesticide formulations containing microcapsules |
HK10103358.8A HK1134890A1 (en) | 2006-11-23 | 2010-04-01 | Novel agrochemical formulations containing microcapsules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP06024299.7 | 2006-11-23 | ||
EP06024299.7A EP1844653B1 (en) | 2006-03-30 | 2006-11-23 | Novel agrochemical formulations containing microcapsules |
Publications (3)
Publication Number | Publication Date |
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WO2008061721A2 true WO2008061721A2 (en) | 2008-05-29 |
WO2008061721A3 WO2008061721A3 (en) | 2009-04-09 |
WO2008061721A4 WO2008061721A4 (en) | 2009-07-09 |
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PCT/EP2007/010073 WO2008061721A2 (en) | 2006-11-23 | 2007-11-21 | Novel agrochemical formulations containing microcapsules |
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Country | Link |
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US (1) | US8263530B2 (en) |
CN (1) | CN101583269B (en) |
AU (1) | AU2007323316B2 (en) |
BR (1) | BRPI0719120A8 (en) |
CA (1) | CA2669478C (en) |
CO (1) | CO6210769A2 (en) |
CR (2) | CR10887A (en) |
HK (1) | HK1134890A1 (en) |
MX (1) | MX2009005419A (en) |
RU (1) | RU2421993C2 (en) |
WO (1) | WO2008061721A2 (en) |
ZA (1) | ZA200903220B (en) |
Cited By (9)
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GB2483052A (en) * | 2010-08-17 | 2012-02-29 | Rotam Agrochem Int Co Ltd | A herbicidal composition comprising an aqueous suspension of microcapsules containing a solution of fluroxypyr in a rosin solvent system |
US8263530B2 (en) | 2006-11-23 | 2012-09-11 | Gat Microencapsulation Ag | Agrochemical formulations containing microcapsules |
EP2615912A2 (en) * | 2010-09-17 | 2013-07-24 | Dow AgroSciences LLC | Liquid agricultural formulations of improved stability |
EP2908645A4 (en) * | 2012-09-04 | 2016-04-27 | Dow Agrosciences Llc | Compositions and methods for improving the compatibility of water soluble herbicide salts |
WO2017220680A1 (en) | 2016-06-21 | 2017-12-28 | Battelle Uk Limited | Liquid sulfonylurea- and li-salt containing herbicidal compositions |
EP3387904A1 (en) | 2014-12-22 | 2018-10-17 | Mitsui AgriScience International S.A./N.V. | Liquid sulfonylurea-containing herbicidal compositions |
WO2020025566A1 (en) * | 2018-07-31 | 2020-02-06 | Bayer Aktiengesellschaft | Capsule suspensions with agrochemical active ingredients |
WO2021152391A1 (en) | 2020-01-29 | 2021-08-05 | Fmc Agricultural Caribe Industries Ltd. | Liquid sulfonylurea compositions |
EP3900535A1 (en) | 2020-04-24 | 2021-10-27 | Battelle UK Limited | Liquid sulfonylurea herbicide composition |
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US10342230B2 (en) * | 2010-02-03 | 2019-07-09 | Upl Limited | ZC composition comprising microencapsulated pendimethalin |
GB2483050B (en) * | 2010-08-17 | 2012-12-19 | Rotam Agrochem Int Co Ltd | Herbicidal compositions |
CN102217625A (en) * | 2011-05-06 | 2011-10-19 | 浙江泰达作物科技有限公司 | Mesosulfuron and ethoxysulfuron complex herbicide suspending agent and preparation method thereof |
CN102599165A (en) * | 2012-02-21 | 2012-07-25 | 广东中迅农科股份有限公司 | Azoxystrobin microcapsule suspending agent and preparation method thereof |
GB2497901B (en) * | 2013-04-12 | 2016-03-02 | Rotam Agrochem Int Co Ltd | A herbicide composition comprising clomazone encapsulated within cross-linked polyacetylene carbamide-polyurea microcapsules |
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CN104304261A (en) * | 2014-09-25 | 2015-01-28 | 南京华洲药业有限公司 | Mixed herbicide containing diflufenican and triaziflam and preparation method thereof |
CN104430457B (en) * | 2014-11-30 | 2016-07-06 | 南京华洲药业有限公司 | A kind of mixed herbicide containing flazasulfuron, fluroxypyr and Flumetsulam |
CN105410015B (en) * | 2015-12-25 | 2018-08-21 | 山东潍坊润丰化工股份有限公司 | A kind of chlopyrifos water dispersible granules and preparation method thereof |
EP3405030B1 (en) * | 2016-01-22 | 2020-11-04 | Basf Se | Biodegradable polyester capsules comprising an aqueous core and a pesticide |
CN109414013B (en) * | 2016-07-27 | 2021-11-12 | 巴斯夫欧洲公司 | Having an anion C6-C10Agroformulation of co-dispersant microcapsules |
HUE058324T2 (en) * | 2017-03-17 | 2022-07-28 | Corteva Agriscience Llc | Microencapsulated nitrification inhibitor compositions |
CN111972422B (en) * | 2019-05-21 | 2022-10-25 | 江苏龙灯化学有限公司 | Weeding composition containing microcapsules and preparation method and application thereof |
CN112841216B (en) * | 2020-12-31 | 2022-07-12 | 山东观变生物科技有限公司 | Chlorine dioxide liquid microcapsule and preparation method thereof |
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- 2007-11-21 AU AU2007323316A patent/AU2007323316B2/en not_active Ceased
- 2007-11-21 CA CA2669478A patent/CA2669478C/en not_active Expired - Fee Related
- 2007-11-21 US US12/312,644 patent/US8263530B2/en active Active
- 2007-11-21 BR BRPI0719120A patent/BRPI0719120A8/en not_active Application Discontinuation
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Cited By (17)
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US8263530B2 (en) | 2006-11-23 | 2012-09-11 | Gat Microencapsulation Ag | Agrochemical formulations containing microcapsules |
GB2483052B (en) * | 2010-08-17 | 2012-12-19 | Rotam Agrochem Int Co Ltd | Herbicidal compositions |
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Also Published As
Publication number | Publication date |
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CN101583269A (en) | 2009-11-18 |
CA2669478C (en) | 2016-06-14 |
RU2009120935A (en) | 2010-12-27 |
RU2421993C2 (en) | 2011-06-27 |
WO2008061721A4 (en) | 2009-07-09 |
CR10887A (en) | 2009-10-26 |
ZA200903220B (en) | 2010-03-31 |
AU2007323316A2 (en) | 2011-05-26 |
AU2007323316A1 (en) | 2008-05-29 |
CR20140254A (en) | 2014-06-16 |
BRPI0719120A2 (en) | 2015-09-15 |
US8263530B2 (en) | 2012-09-11 |
CO6210769A2 (en) | 2010-10-20 |
HK1134890A1 (en) | 2010-05-20 |
AU2007323316B2 (en) | 2012-12-06 |
CA2669478A1 (en) | 2008-05-29 |
US20100056373A1 (en) | 2010-03-04 |
CN101583269B (en) | 2014-08-27 |
WO2008061721A3 (en) | 2009-04-09 |
BRPI0719120A8 (en) | 2017-07-11 |
MX2009005419A (en) | 2009-07-06 |
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