CA1285785C - Aqueous emulsions of plant protection agents - Google Patents
Aqueous emulsions of plant protection agentsInfo
- Publication number
- CA1285785C CA1285785C CA000524055A CA524055A CA1285785C CA 1285785 C CA1285785 C CA 1285785C CA 000524055 A CA000524055 A CA 000524055A CA 524055 A CA524055 A CA 524055A CA 1285785 C CA1285785 C CA 1285785C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- agent
- ethyl
- methyl
- group
- 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.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 16
- 239000011814 protection agent Substances 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- -1 alkyl phenoxyphenoxypropionates Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- RDYMFSUJUZBWLH-SVWSLYAFSA-N endosulfan Chemical compound C([C@@H]12)OS(=O)OC[C@@H]1[C@]1(Cl)C(Cl)=C(Cl)[C@@]2(Cl)C1(Cl)Cl RDYMFSUJUZBWLH-SVWSLYAFSA-N 0.000 claims description 7
- JOOMJVFZQRQWKR-UHFFFAOYSA-N pyrazophos Chemical compound N1=C(C)C(C(=O)OCC)=CN2N=C(OP(=S)(OCC)OCC)C=C21 JOOMJVFZQRQWKR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- PQKBPHSEKWERTG-UHFFFAOYSA-N Fenoxaprop ethyl Chemical group C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-UHFFFAOYSA-N 0.000 claims description 6
- NEKOXWSIMFDGMA-UHFFFAOYSA-N Isopropalin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(C)C)C=C1[N+]([O-])=O NEKOXWSIMFDGMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ZRDUSMYWDRPZRM-UHFFFAOYSA-N 2-sec-butyl-4,6-dinitrophenyl 3-methylbut-2-enoate Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)C=C(C)C ZRDUSMYWDRPZRM-UHFFFAOYSA-N 0.000 claims description 5
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 239000004009 herbicide Substances 0.000 claims description 5
- 239000002917 insecticide Substances 0.000 claims description 5
- 239000003016 pheromone Substances 0.000 claims description 5
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 claims description 4
- YEGGTTBLVORABJ-UXBLZVDNSA-N (2-butan-2-yl-4,6-dinitrophenyl) (e)-2-methylbut-2-enoate Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)C(\C)=C\C YEGGTTBLVORABJ-UXBLZVDNSA-N 0.000 claims description 3
- YHLDGLRUQIOFGR-UHFFFAOYSA-N 2,6-dibromo-4-hydroxybenzonitrile;octanoic acid Chemical compound CCCCCCCC(O)=O.OC1=CC(Br)=C(C#N)C(Br)=C1 YHLDGLRUQIOFGR-UHFFFAOYSA-N 0.000 claims description 3
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical class OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 claims description 3
- HFOFYNMWYRXIBP-MOPGFXCFSA-N 2-methyl-7S,8R-Epoxy-octadecane Chemical compound CCCCCCCCCC[C@H]1O[C@H]1CCCCC(C)C HFOFYNMWYRXIBP-MOPGFXCFSA-N 0.000 claims description 3
- 239000005892 Deltamethrin Substances 0.000 claims description 3
- IIPZYDQGBIWLBU-UHFFFAOYSA-N Dinoterb Chemical compound CC(C)(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O IIPZYDQGBIWLBU-UHFFFAOYSA-N 0.000 claims description 3
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 claims description 3
- 229960002483 decamethrin Drugs 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- HVCNNTAUBZIYCG-UHFFFAOYSA-N ethyl 2-[4-[(6-chloro-1,3-benzothiazol-2-yl)oxy]phenoxy]propanoate Chemical compound C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2S1 HVCNNTAUBZIYCG-UHFFFAOYSA-N 0.000 claims description 3
- 230000002363 herbicidal effect Effects 0.000 claims description 3
- BACHBFVBHLGWSL-UHFFFAOYSA-N methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 claims description 3
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000855 fungicidal effect Effects 0.000 claims 2
- 239000000417 fungicide Substances 0.000 claims 2
- LZGUHMNOBNWABZ-UHFFFAOYSA-N n-nitro-n-phenylnitramide Chemical class [O-][N+](=O)N([N+]([O-])=O)C1=CC=CC=C1 LZGUHMNOBNWABZ-UHFFFAOYSA-N 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 29
- 239000000203 mixture Substances 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 10
- 229920001400 block copolymer Polymers 0.000 abstract description 10
- 238000009472 formulation Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- 229940117927 ethylene oxide Drugs 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229940093476 ethylene glycol Drugs 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229920001522 polyglycol ester Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 1
- MHKBMNACOMRIAW-UHFFFAOYSA-N 2,3-dinitrophenol Chemical class OC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O MHKBMNACOMRIAW-UHFFFAOYSA-N 0.000 description 1
- SGBQUMZTGSQNAO-UHFFFAOYSA-N 2-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(O)=CC=C21 SGBQUMZTGSQNAO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940093470 ethylene Drugs 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 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
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940095050 propylene Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Toxicology (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the disclosure:
The invention describes plant protection agents based on aqueous emulsions and, in addition to the active compound, containing, as the dispersing agent, an ethylene oxide/
propylene oxide/ethylene oxide block copolymer which is phosphorylated in the alpha-position and the omega-posi-tion, or a salt thereof. These formulations have a low solvent content and possess a high stability.
The invention describes plant protection agents based on aqueous emulsions and, in addition to the active compound, containing, as the dispersing agent, an ethylene oxide/
propylene oxide/ethylene oxide block copolymer which is phosphorylated in the alpha-position and the omega-posi-tion, or a salt thereof. These formulations have a low solvent content and possess a high stability.
Description
HOECHST AKTIENGESELLSCHAFT HOE 85/F 269 Dr.AU/ml New aqueous emulsions of plant protection agents It is known, and described in European Patent Application 47,396, to prepare concentrated emulsions, stable on storage, of herbicidally active phenoxyalkanecarboxylic acid esters, having an aqueous base, using ester-soluble emulsifiers and water-soluble dispersing agents. The ester-soluble emulsifiers used, if appropriate as a mix-ture with alkylarylsulfonates, are polyethylene glycol esters of fatty acids, polyethylene glycol ethers of fatty alcohols, of glycerides or of alkylphenols and also poly-oxyethylene and polyoxypropylene block polymers. The dispersing agents used are phosphated alkylarylpolyethy-lene oxides, the ammonium, sodium or potassium salts of phosphorylated polystyrylphenylpolyethylene oxide or ethylene oxide condensates of fatty amines.
The amounts of oil-soluble emulsifiers added are between 1.01 and 11.1 parts by weight per 100 parts by weight of phenoxyalkanecarboxylic acid ester. The amounts of dis-persing agent are 0.5 to 5 parts by weight per 100 parts by weight of aqueous solution. Anti-foaming agents based on long-chain alcohols and silicones are added in order to avoid the formation of foam which takes place in this operation.
Attempts to extend the use of the water-soluble ammonium, sodium or potassium salts of phosphorylated alkylarylpoly-ethylene oxides mentioned above to other active compounds than those mentioned in European Patent Application 47,396 result in considerable technical problems in use.
In storage tests of over 3 months at 50C, demixing phe-nomena which are reversible only to a limited extent occur in a number of preparations.
Similar problems are observed with the phosphorylated polystyrylphenylpolyethylene oxides described in European 128~78~
The amounts of oil-soluble emulsifiers added are between 1.01 and 11.1 parts by weight per 100 parts by weight of phenoxyalkanecarboxylic acid ester. The amounts of dis-persing agent are 0.5 to 5 parts by weight per 100 parts by weight of aqueous solution. Anti-foaming agents based on long-chain alcohols and silicones are added in order to avoid the formation of foam which takes place in this operation.
Attempts to extend the use of the water-soluble ammonium, sodium or potassium salts of phosphorylated alkylarylpoly-ethylene oxides mentioned above to other active compounds than those mentioned in European Patent Application 47,396 result in considerable technical problems in use.
In storage tests of over 3 months at 50C, demixing phe-nomena which are reversible only to a limited extent occur in a number of preparations.
Similar problems are observed with the phosphorylated polystyrylphenylpolyethylene oxides described in European 128~78~
Patent Application 33,291; in the same way it is only possible to obtain colloidal emulsions of limited heat stability using alkylaryl polyglycol ether compounds described in DE-A 3,111,934.
Furthermore, it is descr:Lbed in EP-A 118,759 that t.erminally monophosphorylated ethy:Lene oxide/propylene oxide/
ethylene oxide block copolymers or salts thereof can be employed as dispersing agents in order to obtain aqueous pesticide formulations.
It has now been found, surprisingly, that certain wetting and dispersing agents which are soluble in water and organic solvents can be used advantageously in comparison with the water-soluble dispersing agents of the phosphorylated alkylarylpolyethylene oxide type described in EP-A 47,396 and in comparison with the terminally monophosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers described in EP-A 118,759.
The present invention therefore provides a plant protection ayent based on aqueous emulsions containing 5-60~ by weight of one or more active compounds which are soluble in water only to a slight extent or not at all, 10-90'~ by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I
1l (H)2P-[-(CH2-cH2-)x-(cjH-cH2-o)y-(cH2-cH2-o)z] 1 0 CH3 P(OH)m (I) 2 ( 2 CH2-)x-(~H-CH2-)y~(CH2~CH2~) ]
in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.
~?
.~
;,; ;. .
- 12857~
-2a- 23221-4322 Suitable salts are, in particular, the alkali metal, alkaline earth metal, ammonium, monoalkylammonium, dialkylammonium or trialkylammonium or monoalkanolammonium, dialkanolammonium or trialkanolammonium salts. These contain, in particular, 1 to 5 carbon atoms in the alkyl or alkanol moiety, respectively.
The preparations according to the invention are substantially free from organic solvents and inorganic salts.
They can therefore be handlecl without risk, especially in transport and storage. The viscosity of the finished preparation can be adjusted witlout problems to the desired r;
Furthermore, it is descr:Lbed in EP-A 118,759 that t.erminally monophosphorylated ethy:Lene oxide/propylene oxide/
ethylene oxide block copolymers or salts thereof can be employed as dispersing agents in order to obtain aqueous pesticide formulations.
It has now been found, surprisingly, that certain wetting and dispersing agents which are soluble in water and organic solvents can be used advantageously in comparison with the water-soluble dispersing agents of the phosphorylated alkylarylpolyethylene oxide type described in EP-A 47,396 and in comparison with the terminally monophosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers described in EP-A 118,759.
The present invention therefore provides a plant protection ayent based on aqueous emulsions containing 5-60~ by weight of one or more active compounds which are soluble in water only to a slight extent or not at all, 10-90'~ by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I
1l (H)2P-[-(CH2-cH2-)x-(cjH-cH2-o)y-(cH2-cH2-o)z] 1 0 CH3 P(OH)m (I) 2 ( 2 CH2-)x-(~H-CH2-)y~(CH2~CH2~) ]
in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.
~?
.~
;,; ;. .
- 12857~
-2a- 23221-4322 Suitable salts are, in particular, the alkali metal, alkaline earth metal, ammonium, monoalkylammonium, dialkylammonium or trialkylammonium or monoalkanolammonium, dialkanolammonium or trialkanolammonium salts. These contain, in particular, 1 to 5 carbon atoms in the alkyl or alkanol moiety, respectively.
The preparations according to the invention are substantially free from organic solvents and inorganic salts.
They can therefore be handlecl without risk, especially in transport and storage. The viscosity of the finished preparation can be adjusted witlout problems to the desired r;
value by varying the polyethylene glycol content, so that it is possible to dispense with the dlspersing and thickening agents which are otherwise customary.
5uitahle phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers to be used in accordance with the invention are, in particular, those of the formula I and salts thereof:
(HO)2~-[O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z] O
CH3 P(OH)m (I) [(HO)2~-O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z]n in which x, y and z independently of one another denote a number from 2 to 200 and m and n denote 0, 1 or 2, it being necessary for the sum of n ~ m to be 2.
Preferably, x and z have the same meaning and represent, in particular, a number from 30 to 100; y denotes, in particular, a number from 20 to 100 and n is, in particular, 0. These block polymers can be employed ln the form of mixtures. Their preparation is described in Japanese Laid Open Patent Application JP-A-72/47982 t1972) of Kanebo & Co. Ltd. or in German Offenlegungsschrift No. 3,542,441 of June 4, 1987 (priority November 30, 1985) of Hoechst Aktiengesellschaft.
The formulations according to the invention can also contain, in addition, anti-freezing agents. These include, for example: ethylene glycol, propylene glycol, butanediol, urea, glycerol, polyethylene glycols and polypropylene glycols. They can also contain further formulation auxiliaries, such as ~28S785 -3a- 23221-4322 customary dlspersing agents, emulsifiers, thickeners and -especially for solid active compounds - also minor constituents of organic solvents.
Active compounds which can be employed for these preparations are, in particular, those which, by virtue of their low mel~ing point, can only be converted with difficulty or not at all into a finely disperse aqueous phase by lZ8~
means of grinding devices, or those in the case of which the grinding process demands special safety precautions.
Suitable active compounds for plant protection agents which can be employed are herbicides, insecticides, acari-cides, nematocides, pheromones or repellents, it being necessary for these to be soluble in water only to a slight extent or not at all. Solid active compounds should, however, have a good to very good solubility in one of the organic solvents mentioned below.
ExampLes of suitable herbicidal active compounds are alkyl phenoxyphenoxypropionates or alkyl heteroaryloxyphenoxy-propionates, such as methyl ~-4-(2',4'-dichlorophenoxy)-phenoxypropionate [common name: diclofopmethyl] (A), ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate (B) or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate [common name: fenoxapropethyl] (C), dinitroaniline com-pounds, such as 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline [common name: trifluralin] (D) or 2,6-dinitro-4-isopropyl-N,N-dipropylaniline Ccommon name: isopropa-lin] (E), hydroxybenzonitrile derivatives, such as 2,6-dibromo-4-hydroxybenzonitrile octanoate (F), or dinitro-phenol compounds, such as 2-sec.-butyl-4,6-dinitrophenol Ccommon name: dinoterb] (G).
The following are examples of suitable insecticides:
1,4,5,6,7,7-hexachloro-8,9,1û-trinorborn-5-en-2,3-ylene dimethyl sulfite [common name: endosulfan], 2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate Ccommon name: binapacryl], phosphoric acid esters, such as 0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate Ccommon name: triazophos] or pyrethroids, such as (S)-~-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dibromovinyl) 2,2-dimethylcyclopropanecarboxylate [common name: deltame-thrin].
Ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazoloC1,5a]-128578~i pyrim;d;ne-6-carboxylate [common name: pyrazophos] should be ment;oned as an example of suitable fungic;des, and the compounds (E)-8-(E)-10-dodecadienol or (Z)-7,8-epoxy-2-methyloctadecane should be mentioned as pheromones, and dimethyL phthalate should be mentioned as an example of repellents.
With the exception of the compounds (B) and (C), the abovementioned herbicides and the insecticides and the repellent are known from H. Martin, Pesticide Manual 6th edition 1979. The herbicides B) and C) are described in German Offenlegungsschrift 2,640,730, and the two phero-mones in M. Beroza, Chem. Controlling Insect Behaviour, Academic Press, N.Y. 1970.
Customary dispersing agents which may be employed in par-t;cular cases are preferably lignosulfonates, Na salts of dinaphthylmethanedisulfonic acids, the Na salt of a sul-fon;c ac;d formed from cresol, formaldehyde, Na sulfite and hydroxynaphthalenesulfonic acid, the Na salt of a sulfonic acid formed from m-cresol, formaldehyde and Na sulfite, condensation products formed from arylsulfonic acids and formaldehyde-Na salts, triethanolam;ne salts of phosphorylated polystyrylphenylpolyethylene oxides, poly-v;nyl alcohol, calcium dodecylbenzenesulfonate and alkyl-naphthalenesulfonates of vary;ng alkyl chain length.
Su;table emulsifiers are nonionic, anionic or cationic surface-active substances, mixtures of nonionic and anionic components being used predominantly. Combinations of nonion;c and cat;on;c surface-act;ve agents can also be used, however. The emuls;f;ers which can be employed preferentially ;nclude calc;um phenylsulfonate, ethoxy-lated nonylphenols, ethoxylated aliphatic alcohols, ethoxylated castor oil, polyglycol esters of fatty acids, propylene glycol/ethylene glycol block polymers and mix-tures thereof.
Water-soluble polymers, such as, for example, polyvinyl 12~s7~;
alcohol, polyvinylpyrrolidone and cellulose der;vatives, can be used as thickening agents.
Suitable organic solvents are any water-immiscible sol-vents, for example aromatic compounds, such as toluene, xylenes, 1/2 methylnaphthylene or dimethylnaphthalenes, aliphatic compounds, such as paraffin oils or vegetable oils, alicyclic compounds, such as cyclohexane, alkanols, such as cyclohexanol or i-octyl alcohol, ethers, such as diethyl ether, ketones, such as cyclohexanone, 4-methyl-cyclohexanone or isophorone, or esters, such as ethyl acetate and tri-n-butyl phosphate.
The plant protection agents according to the invention contain, in particular, 5-60% by weight of active com-pound, 10-90% by weight, preferably 15-40% by weight, of water and 0.5-20% by weight, preferably 1-10% by weight, of a compound of the formula I or salts thereof, and cus-tomary additives, if appropriate 5 to 50% by weight of an Z0 anti-freezing agent and/or 1-10% by weight of a dispers-ing agent and/or 1-15% by weight of an emulsifier and/or 1-10% by we;ght of a thickener and/or 1 to 30% by weight of an organic solvent.
The invention also relates to a process for the prepara-tion of the agents according to the invention. For this purpose, the abovementioned components are stirred or shaken, in the required amounts, at temperatures between 0 and 60C, preferably at room temperature, in a zone of high turbulence until the desired stable emulsion has been formed; in the course of this the particle diameter is adjusted to, preferably, 1-15 ~m.
In order to carry out the process in practice, the aque-ous phase (carrier phase) is first prepared by stirring the diols or polyols and the dispersing agent into water.
After this the emusifier component is added to the ac-tive compound to be emulsified, and the mixture is finely dispersed in the aqueous phase. In the case of active compounds having a melting point of approx. 0C and higher, it can be necessary to prepare concentrated solu-tions thereof in one or more of the abovementioned organic solvents and to disperse these solutions in the aqueous phase after adding emulsifiers and, if appropriate, sta-bilizers.
lt is also possible, however, first to mix the dispersing agent into the active compound and then to disperse the mixture into the aqueous phase.
Dispersing can be effected by a stirring process or, if appropriate, also a shaking process, and is preferably continued until the organic phase corresponds to the desired droplet size. A droplet diameter of 1-15 ~m is advisable. The dispersing process is preferably carried out at room temperature, but can, however, also be carried out under cold conditions or at elevated temperatures.
Z0 The following examples are intended to illustrate the present invention in greater detail.
Formulation examples Example 1 36X by we;ght of methyl 2-(4-(2',4'-dichlorophenoxy)-phenoxy)-propionate are dissolved by stirring in 18% by weight of xylene at 20-25C, and 6~ by weight of a polygly-col fatty acid ester (containing 40 E0) are added. 2% byweight of the potassium salt of the phosphorylated ethy-lene oxide/propylene oxide/ethylene oxide block polymer of the abovementioned formula 1, n = 0 (containing 68% of ethylene oxide in the end product) are also dissolved in 28% by weight of water at room temperature, and 10% by weight of ethylene glycol are then added. The abovemen-tioned organic phase is allowed to flow slowly into this aqueous phase, with vigorous stirring by means of a blade stirrer, and the resulting white emulsion is stirred for 128~
approx. 15 minutes further. One sample is stored for 3 months at 50C; another is stored for the same period at -10C. The preparation is stable both to chemicals and in use.
s Example 2 32.3% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 4~ by weight of the diethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (containing 55% of ethylene oxide in the end product) are added. 8% by weight of glycerol are dissolved at room temperature in 34.7% by weight of water. The organic phase is allowed to flow slowly into this solution, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 minutes further.
The preparation is stable to chemicals and in use.
Example 3 30% by weight of ethyl 2-diethoxythiophosphoryloxy-5-methylpyrazolo[1,5a]pyrimidine-6-carboxylate (pyrazophos) are dissolved, with stirring and at 20-25C, in 18% by weight of xylene, and 6% by weight of a polyglycol ester (containing 40 EO) are added~ 4% by weight of the pota-sium salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I, n = o (containing 50% of ethylene oxide in the end product), are also dissolved at room temperature in 32% by weight of water, and 10% by weight of ethylene gly-col are then added. The abovementioned organic phase is allowed to flow slowly, with vigorous stirring by means of a paddle stirrer, into this aqueous phase, and the resulting white emulsion is stirred for approx. 15 minutes further. One sample is stored for 3 months at 50C;
another is stored for the same period at -10C. The lZ8~;785 g preparation is stable both to chemicals and in use.
Example 4 6.0% by weight of a polyglycol fatty acid ester (36 E0), 3% by weight of the free acid of the phosPhoryLated ethy-lene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (having a total content of 40% of ethylene oxide) and 10% by weight of glycerol are disso-lved in 49% by weight of water. 32.û% by weight of (E)-8-(E)-10-dodecadienol are then run in, with vigor-ous stirring. The resulting white emulsion is stirred for a further 15 to 20 minutes.
The preparation is stable to chemicals and in use.
Example 5 30.0% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 3% by weight of the free acid of the phosphorylated ethylene oxide/propy-lene oxide/ethylene oxide block copolymer of the above-mentioned formula I (containing 55% of ethylene oxide in the end product) are added. 12% by weight of polyethylene glycol (MW 1,000) are dissolved at room temperature in 34.0% by weight of water. The organic Phase is then run in slowly, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 min-utes further.
~he preparation is stable to chemicals and in use.
Example 6 3520% by weight of ethyl Z-(4-(6-chlor-2-benzothiazolyloxy)-phenoxypropanoate are dissolved in 36% by weight of xylene at 40-45C, with stirring, and 4% by weight of the potas-sium salt of the phosphorylated ethylene oxide/propylene --- 12B578~i oxide/ethylene oxide block copolymer of the formula I, n = o, having a total content of 6û% of ethylene oxide, and 2% by we;ght of the triethanolamine salt of a phos-phorylated polystyrylphenylpolyethylene oxide and 4% by weight of calcium dodecylbenzenesulfonate are added.
9% by weight of ethylene glycol are dissolved at room tem-perature in 25% by weight of water. The abovementioned organic phase is run into this aqueous solution, with vigorous stirring by means of a paddle stirrerj and the resulting white emulsion is stirred for approx. 15 minutes further at room temperature. A sample is stored for 3 months at 50C. The preparation is stable to chemicals and in use.
Example 7 35% by weight of 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline (trifluralin) are dissolved in 20% by weight of xylene at 20-25C, with stirring, and 3% by weight of the triethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the formula I (containing 55% of ethylene oxide) and 2%
by weight of the triethanolamine salt of a phosphorylated polystyrylphenylpolyethylene oxide and 3% by weight of a polyglycol fatty acid ester (36 E0) are added. 6% by we;ght of polypropylene glycol (molecular weight S00) are dissolved at room temperature in 31% by weight of water.
The organic phase is allowed to flow slowly into this aqueous solution, with vigorous stirring, and the result-ing yellow emulsion is stirred for approx. 20-25 minutes further, until the pale yellow color shade of the emulsion undergoes no further change. The preparation is stable in use and to chemicals even after storage at various temperatures.
5uitahle phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymers to be used in accordance with the invention are, in particular, those of the formula I and salts thereof:
(HO)2~-[O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z] O
CH3 P(OH)m (I) [(HO)2~-O-(CH2-CH2-O)X-(CH-CH2-O)y-(CH2-CH2-O)z]n in which x, y and z independently of one another denote a number from 2 to 200 and m and n denote 0, 1 or 2, it being necessary for the sum of n ~ m to be 2.
Preferably, x and z have the same meaning and represent, in particular, a number from 30 to 100; y denotes, in particular, a number from 20 to 100 and n is, in particular, 0. These block polymers can be employed ln the form of mixtures. Their preparation is described in Japanese Laid Open Patent Application JP-A-72/47982 t1972) of Kanebo & Co. Ltd. or in German Offenlegungsschrift No. 3,542,441 of June 4, 1987 (priority November 30, 1985) of Hoechst Aktiengesellschaft.
The formulations according to the invention can also contain, in addition, anti-freezing agents. These include, for example: ethylene glycol, propylene glycol, butanediol, urea, glycerol, polyethylene glycols and polypropylene glycols. They can also contain further formulation auxiliaries, such as ~28S785 -3a- 23221-4322 customary dlspersing agents, emulsifiers, thickeners and -especially for solid active compounds - also minor constituents of organic solvents.
Active compounds which can be employed for these preparations are, in particular, those which, by virtue of their low mel~ing point, can only be converted with difficulty or not at all into a finely disperse aqueous phase by lZ8~
means of grinding devices, or those in the case of which the grinding process demands special safety precautions.
Suitable active compounds for plant protection agents which can be employed are herbicides, insecticides, acari-cides, nematocides, pheromones or repellents, it being necessary for these to be soluble in water only to a slight extent or not at all. Solid active compounds should, however, have a good to very good solubility in one of the organic solvents mentioned below.
ExampLes of suitable herbicidal active compounds are alkyl phenoxyphenoxypropionates or alkyl heteroaryloxyphenoxy-propionates, such as methyl ~-4-(2',4'-dichlorophenoxy)-phenoxypropionate [common name: diclofopmethyl] (A), ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate (B) or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate [common name: fenoxapropethyl] (C), dinitroaniline com-pounds, such as 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline [common name: trifluralin] (D) or 2,6-dinitro-4-isopropyl-N,N-dipropylaniline Ccommon name: isopropa-lin] (E), hydroxybenzonitrile derivatives, such as 2,6-dibromo-4-hydroxybenzonitrile octanoate (F), or dinitro-phenol compounds, such as 2-sec.-butyl-4,6-dinitrophenol Ccommon name: dinoterb] (G).
The following are examples of suitable insecticides:
1,4,5,6,7,7-hexachloro-8,9,1û-trinorborn-5-en-2,3-ylene dimethyl sulfite [common name: endosulfan], 2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate Ccommon name: binapacryl], phosphoric acid esters, such as 0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate Ccommon name: triazophos] or pyrethroids, such as (S)-~-cyano-3-phenoxybenzyl-(lR,3R)-3-(2,2-dibromovinyl) 2,2-dimethylcyclopropanecarboxylate [common name: deltame-thrin].
Ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazoloC1,5a]-128578~i pyrim;d;ne-6-carboxylate [common name: pyrazophos] should be ment;oned as an example of suitable fungic;des, and the compounds (E)-8-(E)-10-dodecadienol or (Z)-7,8-epoxy-2-methyloctadecane should be mentioned as pheromones, and dimethyL phthalate should be mentioned as an example of repellents.
With the exception of the compounds (B) and (C), the abovementioned herbicides and the insecticides and the repellent are known from H. Martin, Pesticide Manual 6th edition 1979. The herbicides B) and C) are described in German Offenlegungsschrift 2,640,730, and the two phero-mones in M. Beroza, Chem. Controlling Insect Behaviour, Academic Press, N.Y. 1970.
Customary dispersing agents which may be employed in par-t;cular cases are preferably lignosulfonates, Na salts of dinaphthylmethanedisulfonic acids, the Na salt of a sul-fon;c ac;d formed from cresol, formaldehyde, Na sulfite and hydroxynaphthalenesulfonic acid, the Na salt of a sulfonic acid formed from m-cresol, formaldehyde and Na sulfite, condensation products formed from arylsulfonic acids and formaldehyde-Na salts, triethanolam;ne salts of phosphorylated polystyrylphenylpolyethylene oxides, poly-v;nyl alcohol, calcium dodecylbenzenesulfonate and alkyl-naphthalenesulfonates of vary;ng alkyl chain length.
Su;table emulsifiers are nonionic, anionic or cationic surface-active substances, mixtures of nonionic and anionic components being used predominantly. Combinations of nonion;c and cat;on;c surface-act;ve agents can also be used, however. The emuls;f;ers which can be employed preferentially ;nclude calc;um phenylsulfonate, ethoxy-lated nonylphenols, ethoxylated aliphatic alcohols, ethoxylated castor oil, polyglycol esters of fatty acids, propylene glycol/ethylene glycol block polymers and mix-tures thereof.
Water-soluble polymers, such as, for example, polyvinyl 12~s7~;
alcohol, polyvinylpyrrolidone and cellulose der;vatives, can be used as thickening agents.
Suitable organic solvents are any water-immiscible sol-vents, for example aromatic compounds, such as toluene, xylenes, 1/2 methylnaphthylene or dimethylnaphthalenes, aliphatic compounds, such as paraffin oils or vegetable oils, alicyclic compounds, such as cyclohexane, alkanols, such as cyclohexanol or i-octyl alcohol, ethers, such as diethyl ether, ketones, such as cyclohexanone, 4-methyl-cyclohexanone or isophorone, or esters, such as ethyl acetate and tri-n-butyl phosphate.
The plant protection agents according to the invention contain, in particular, 5-60% by weight of active com-pound, 10-90% by weight, preferably 15-40% by weight, of water and 0.5-20% by weight, preferably 1-10% by weight, of a compound of the formula I or salts thereof, and cus-tomary additives, if appropriate 5 to 50% by weight of an Z0 anti-freezing agent and/or 1-10% by weight of a dispers-ing agent and/or 1-15% by weight of an emulsifier and/or 1-10% by we;ght of a thickener and/or 1 to 30% by weight of an organic solvent.
The invention also relates to a process for the prepara-tion of the agents according to the invention. For this purpose, the abovementioned components are stirred or shaken, in the required amounts, at temperatures between 0 and 60C, preferably at room temperature, in a zone of high turbulence until the desired stable emulsion has been formed; in the course of this the particle diameter is adjusted to, preferably, 1-15 ~m.
In order to carry out the process in practice, the aque-ous phase (carrier phase) is first prepared by stirring the diols or polyols and the dispersing agent into water.
After this the emusifier component is added to the ac-tive compound to be emulsified, and the mixture is finely dispersed in the aqueous phase. In the case of active compounds having a melting point of approx. 0C and higher, it can be necessary to prepare concentrated solu-tions thereof in one or more of the abovementioned organic solvents and to disperse these solutions in the aqueous phase after adding emulsifiers and, if appropriate, sta-bilizers.
lt is also possible, however, first to mix the dispersing agent into the active compound and then to disperse the mixture into the aqueous phase.
Dispersing can be effected by a stirring process or, if appropriate, also a shaking process, and is preferably continued until the organic phase corresponds to the desired droplet size. A droplet diameter of 1-15 ~m is advisable. The dispersing process is preferably carried out at room temperature, but can, however, also be carried out under cold conditions or at elevated temperatures.
Z0 The following examples are intended to illustrate the present invention in greater detail.
Formulation examples Example 1 36X by we;ght of methyl 2-(4-(2',4'-dichlorophenoxy)-phenoxy)-propionate are dissolved by stirring in 18% by weight of xylene at 20-25C, and 6~ by weight of a polygly-col fatty acid ester (containing 40 E0) are added. 2% byweight of the potassium salt of the phosphorylated ethy-lene oxide/propylene oxide/ethylene oxide block polymer of the abovementioned formula 1, n = 0 (containing 68% of ethylene oxide in the end product) are also dissolved in 28% by weight of water at room temperature, and 10% by weight of ethylene glycol are then added. The abovemen-tioned organic phase is allowed to flow slowly into this aqueous phase, with vigorous stirring by means of a blade stirrer, and the resulting white emulsion is stirred for 128~
approx. 15 minutes further. One sample is stored for 3 months at 50C; another is stored for the same period at -10C. The preparation is stable both to chemicals and in use.
s Example 2 32.3% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 4~ by weight of the diethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (containing 55% of ethylene oxide in the end product) are added. 8% by weight of glycerol are dissolved at room temperature in 34.7% by weight of water. The organic phase is allowed to flow slowly into this solution, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 minutes further.
The preparation is stable to chemicals and in use.
Example 3 30% by weight of ethyl 2-diethoxythiophosphoryloxy-5-methylpyrazolo[1,5a]pyrimidine-6-carboxylate (pyrazophos) are dissolved, with stirring and at 20-25C, in 18% by weight of xylene, and 6% by weight of a polyglycol ester (containing 40 EO) are added~ 4% by weight of the pota-sium salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I, n = o (containing 50% of ethylene oxide in the end product), are also dissolved at room temperature in 32% by weight of water, and 10% by weight of ethylene gly-col are then added. The abovementioned organic phase is allowed to flow slowly, with vigorous stirring by means of a paddle stirrer, into this aqueous phase, and the resulting white emulsion is stirred for approx. 15 minutes further. One sample is stored for 3 months at 50C;
another is stored for the same period at -10C. The lZ8~;785 g preparation is stable both to chemicals and in use.
Example 4 6.0% by weight of a polyglycol fatty acid ester (36 E0), 3% by weight of the free acid of the phosPhoryLated ethy-lene oxide/propylene oxide/ethylene oxide block copolymer of the abovementioned formula I (having a total content of 40% of ethylene oxide) and 10% by weight of glycerol are disso-lved in 49% by weight of water. 32.û% by weight of (E)-8-(E)-10-dodecadienol are then run in, with vigor-ous stirring. The resulting white emulsion is stirred for a further 15 to 20 minutes.
The preparation is stable to chemicals and in use.
Example 5 30.0% by weight of technical endosulfan are dissolved, with stirring, in 21% by weight of a mixture of aromatic compounds (boiling range 219C-282C), and 3% by weight of the free acid of the phosphorylated ethylene oxide/propy-lene oxide/ethylene oxide block copolymer of the above-mentioned formula I (containing 55% of ethylene oxide in the end product) are added. 12% by weight of polyethylene glycol (MW 1,000) are dissolved at room temperature in 34.0% by weight of water. The organic Phase is then run in slowly, with vigorous stirring, and the resulting beige-colored emulsion is stirred for approx. 15-20 min-utes further.
~he preparation is stable to chemicals and in use.
Example 6 3520% by weight of ethyl Z-(4-(6-chlor-2-benzothiazolyloxy)-phenoxypropanoate are dissolved in 36% by weight of xylene at 40-45C, with stirring, and 4% by weight of the potas-sium salt of the phosphorylated ethylene oxide/propylene --- 12B578~i oxide/ethylene oxide block copolymer of the formula I, n = o, having a total content of 6û% of ethylene oxide, and 2% by we;ght of the triethanolamine salt of a phos-phorylated polystyrylphenylpolyethylene oxide and 4% by weight of calcium dodecylbenzenesulfonate are added.
9% by weight of ethylene glycol are dissolved at room tem-perature in 25% by weight of water. The abovementioned organic phase is run into this aqueous solution, with vigorous stirring by means of a paddle stirrerj and the resulting white emulsion is stirred for approx. 15 minutes further at room temperature. A sample is stored for 3 months at 50C. The preparation is stable to chemicals and in use.
Example 7 35% by weight of 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline (trifluralin) are dissolved in 20% by weight of xylene at 20-25C, with stirring, and 3% by weight of the triethanolamine salt of the phosphorylated ethylene oxide/propylene oxide/ethylene oxide block copolymer of the formula I (containing 55% of ethylene oxide) and 2%
by weight of the triethanolamine salt of a phosphorylated polystyrylphenylpolyethylene oxide and 3% by weight of a polyglycol fatty acid ester (36 E0) are added. 6% by we;ght of polypropylene glycol (molecular weight S00) are dissolved at room temperature in 31% by weight of water.
The organic phase is allowed to flow slowly into this aqueous solution, with vigorous stirring, and the result-ing yellow emulsion is stirred for approx. 20-25 minutes further, until the pale yellow color shade of the emulsion undergoes no further change. The preparation is stable in use and to chemicals even after storage at various temperatures.
Claims (6)
1. A plant protection agent based on aqueous emulsions containing 5-60% by weight of one or more active compounds which are soluble in water only to a slight extent or not at all, 10-90%
by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I
(I) in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.
by weight of water, 0,5-20% by weight of a dispersing agent which is soluble in water and in organic solvent and which is a compound of the formula I
(I) in which x, y and z independently of one another is from 2 to 200, and n and m is 0, 1 or 2 while the sum n + m is 2, and is required, customary additives.
2. An agent as claimed in claim 1, which comprises, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
3. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a herbicide selected from the group consisting of alkyl phenoxyphenoxypropionates or alkyl heteroaryloxyphenoxypropionates, dinitroaniline compounds, hydroxybenzonitrile derivatives or dinitrophenyl compounds, or an insecticide selected from the group consisting of endosulfan, binapacryl, phosphoric acid esters or pyrethroids, or a fungicide, or a pheromone or a repellant.
4. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a herbicide selected from the group consisting of alkyl phenoxyphyhenoxypropionates or alkyl heteroaryloxyphenoxypropionates, dinitroaniline compounds, hydroxybenzonitrile derivatives or dinitrophenyl compounds, or an insecticide selected from the group consisting of endosulfan, binapacryl, phosphoric acid esters or pyrethroids, or a fungicide, or a pheromone or a repellant and, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% hy weight of thickener or 1 - 30% by weight of organic solvent.
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% hy weight of thickener or 1 - 30% by weight of organic solvent.
5. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a compound selected from the group consisting of diclofopmethyl (methyl .alpha.-4-(2',4'-dichlorophenoxy)-phenoxypropionate), fenoxapropethyl (ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate), trifluoralin (2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline), isopropalin (2,6-dinitro-4-isopropyl-N,N-dipropylaniline), 2,6-dibromo-4-hydroxybenzonitrile octanoate, dinoterb (2-sec.-butyl-4,6-dinitrophenol), endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylene dimethyl sulfite), binapacryl (2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate), triazophos (0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate), deltamethrin ((S)-.alpha.-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl)2,2-dimethylcyclopropanecarboxylate), pyrazophos (ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazolo[1,5a]-pyrimidine-6-carboxylate), dimethyl phthalate, (E)-8-(E)-10-dodecadienol or (Z)-7,8-epoxy-2-methyloctadecane.
6. An agent as claimed in claim 1 or 2, which comprises, as the active compound, a compound selected from the group consisting of diclofopmethyl (methyl .alpha.-4-(2',4'-dichlorophenoxy)-phenoxypropionate), fenoxapropethyl (ethyl 2-[4-(6-chloro-2-benzothiazolyloxy)-phenoxy]-propionate or ethyl 2-[4-(6-chloro-2-benzoxazolyloxy)-phenoxy]-propionate), trifluoralin (2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline), isopropalin (2,6-dinitro-4-isopropyl-N,N-dipropylaniline), 2,6-dibromo-4-hydroxybenzonitrile octanoate, dinoterb (2-sec.-butyl-4,6-dinitrophenol), endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylene dimethyl sulfite), binapacryl (2-(1-methyl-n-propyl)-4,6-dinitrophenyl 2-methylcrotonate), triazophos (0,0-diethyl 0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate), deltamethrin (S)-.alpha.-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl) 2,2-dimethylcyclopropanecarboxylate), pyrazophos (ethyl 2-diethoxythiophosphoryloxy-5-methyl-pyrazolo[1,5a]-pyrimidine-6-carboxylate), dimethyl phthalate, (E)-8-(E)-10-dodecadienol or (Z)- 7,8-epoxy-2-methyloctadecane and, in addition, one or more of the following additives:
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
- 50% by weight of anti-freezing agent, 1 - 10% by weight of dispersing agent, 1 - 15% by weight of emulsifier, 1 - 10% by weight of thickener or 1 - 30% by weight of organic solvent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853542439 DE3542439A1 (en) | 1985-11-30 | 1985-11-30 | NEW AQUEOUS PLANT PROTECTION EMULSIONS |
DEP3542439.7 | 1985-11-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1285785C true CA1285785C (en) | 1991-07-09 |
Family
ID=6287311
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000524055A Expired - Lifetime CA1285785C (en) | 1985-11-30 | 1986-11-28 | Aqueous emulsions of plant protection agents |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0224846B1 (en) |
JP (1) | JP2581682B2 (en) |
AR (1) | AR243318A1 (en) |
AT (1) | ATE57061T1 (en) |
AU (1) | AU597314B2 (en) |
CA (1) | CA1285785C (en) |
CZ (1) | CZ416891A3 (en) |
DE (2) | DE3542439A1 (en) |
DK (1) | DK174127B1 (en) |
GR (1) | GR3001158T3 (en) |
HU (1) | HU202714B (en) |
PL (1) | PL262649A1 (en) |
SK (1) | SK416891A3 (en) |
ZA (1) | ZA869001B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3542440A1 (en) * | 1985-11-30 | 1987-06-04 | Hoechst Ag | NEW WATER DISPERSIBLE GRANULES |
FR2643223B1 (en) * | 1989-02-17 | 1991-12-13 | Roussel Uclaf | NOVEL CONCENTRATED AQUEOUS EMULSIONS, THEIR PREPARATION PROCESS AND THEIR APPLICATION IN THE PESTICIDE FIELD |
DE3917959A1 (en) * | 1989-06-02 | 1990-12-06 | Hoechst Ag | LIQUID HERBICIDES |
NZ239522A (en) * | 1990-09-04 | 1993-10-26 | Chapman Chem Co | Pesticidal compositions containing an amine salt of a phosphonic or orthophosphoric acid |
US5674514A (en) * | 1992-09-21 | 1997-10-07 | Ciba-Geigy Corporation | Storage stable pesticidal aqueous emulsions |
US5700472A (en) * | 1992-11-18 | 1997-12-23 | Hoechst Aktiengesellschaft | Oil-in-water emulsions |
DE4343856A1 (en) * | 1993-12-22 | 1995-06-29 | Hoechst Ag | Oil-in-water emulsions |
DE4343857A1 (en) * | 1993-12-22 | 1995-06-29 | Hoechst Ag | Oil-in-water emulsions |
GB9609436D0 (en) * | 1996-05-04 | 1996-07-10 | Zeneca Ltd | Composition and use |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4220611A (en) * | 1978-06-29 | 1980-09-02 | Sandoz, Inc. | Polyoxyalkylene bridged phosphate esters |
HU202052B (en) * | 1983-02-11 | 1991-02-28 | Hoechst Ag | Aqueous emulsion-based plant protective compositions |
-
1985
- 1985-11-30 DE DE19853542439 patent/DE3542439A1/en not_active Withdrawn
-
1986
- 1986-11-25 EP EP86116327A patent/EP0224846B1/en not_active Expired - Lifetime
- 1986-11-25 DE DE8686116327T patent/DE3674734D1/en not_active Expired - Lifetime
- 1986-11-25 AT AT86116327T patent/ATE57061T1/en not_active IP Right Cessation
- 1986-11-27 AR AR86306024A patent/AR243318A1/en active
- 1986-11-28 CA CA000524055A patent/CA1285785C/en not_active Expired - Lifetime
- 1986-11-28 DK DK198605734A patent/DK174127B1/en not_active IP Right Cessation
- 1986-11-28 ZA ZA869001A patent/ZA869001B/en unknown
- 1986-11-28 JP JP61282197A patent/JP2581682B2/en not_active Expired - Lifetime
- 1986-11-28 PL PL1986262649A patent/PL262649A1/en unknown
- 1986-11-28 AU AU65821/86A patent/AU597314B2/en not_active Expired
- 1986-11-28 HU HU864940A patent/HU202714B/en unknown
-
1990
- 1990-12-05 GR GR90400917T patent/GR3001158T3/en unknown
-
1991
- 1991-12-30 SK SK4168-91A patent/SK416891A3/en unknown
- 1991-12-30 CZ CS914168A patent/CZ416891A3/en unknown
Also Published As
Publication number | Publication date |
---|---|
ZA869001B (en) | 1987-07-29 |
CZ416891A3 (en) | 1993-07-14 |
EP0224846A1 (en) | 1987-06-10 |
PL262649A1 (en) | 1987-11-30 |
DE3674734D1 (en) | 1990-11-08 |
DK573486A (en) | 1987-05-31 |
ATE57061T1 (en) | 1990-10-15 |
AU597314B2 (en) | 1990-05-31 |
DE3542439A1 (en) | 1987-06-04 |
SK416891A3 (en) | 1994-06-08 |
DK174127B1 (en) | 2002-07-01 |
HUT43228A (en) | 1987-10-28 |
DK573486D0 (en) | 1986-11-28 |
JP2581682B2 (en) | 1997-02-12 |
GR3001158T3 (en) | 1992-06-30 |
JPS62132801A (en) | 1987-06-16 |
HU202714B (en) | 1991-04-29 |
AU6582186A (en) | 1987-06-04 |
EP0224846B1 (en) | 1990-10-03 |
AR243318A1 (en) | 1993-08-31 |
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