IE911004A1 - Liquid pesticide concentrates - Google Patents
Liquid pesticide concentratesInfo
- Publication number
- IE911004A1 IE911004A1 IE100491A IE100491A IE911004A1 IE 911004 A1 IE911004 A1 IE 911004A1 IE 100491 A IE100491 A IE 100491A IE 100491 A IE100491 A IE 100491A IE 911004 A1 IE911004 A1 IE 911004A1
- Authority
- IE
- Ireland
- Prior art keywords
- pesticide concentrate
- concentrate according
- water
- pesticide
- soluble
- Prior art date
Links
- 239000012141 concentrate Substances 0.000 title claims abstract description 59
- 239000007788 liquid Substances 0.000 title claims abstract description 11
- 239000000575 pesticide Substances 0.000 title claims description 32
- 238000009463 water soluble packaging Methods 0.000 claims abstract description 12
- 239000004480 active ingredient Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000005022 packaging material Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 7
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000895 acaricidal effect Effects 0.000 claims description 2
- 239000000642 acaricide Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 239000004009 herbicide Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000002917 insecticide Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920003087 methylethyl cellulose Polymers 0.000 claims description 2
- 230000008635 plant growth Effects 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 230000000361 pesticidal effect Effects 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 235000008504 concentrate Nutrition 0.000 description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 229920000151 polyglycol Polymers 0.000 description 16
- 239000010695 polyglycol Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000005822 Propiconazole Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- -1 ether phosphates Chemical class 0.000 description 5
- 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 5
- 229920002545 silicone oil Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 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 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003090 pesticide formulation Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010499 rapseed oil Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- JSFATNQSLKRBCI-NLORQXDXSA-N 73945-47-8 Chemical compound CCCCCC(O)\C=C\C=C\C\C=C\C\C=C\CCCC(O)=O JSFATNQSLKRBCI-NLORQXDXSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005813 Penconazole Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AAMREJVMBKXGNA-UHFFFAOYSA-N calcium;dodecyl benzoate Chemical compound [Ca].CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 AAMREJVMBKXGNA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical class CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- COYBRKAVBMYYSF-UHFFFAOYSA-N heptan-2-yl [(5-chloroquinolin-8-yl)oxy]acetate Chemical compound C1=CN=C2C(OCC(=O)OC(C)CCCCC)=CC=C(Cl)C2=C1 COYBRKAVBMYYSF-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
-
- 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
-
- 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
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
There are described pesticidal active substance concentrates in packaged form which consist of a water-soluble packaging and a liquid, non-aqueous pesticidal concentrate.
Description
Liquid pesticide concentrates The present invention relates to liquid pesticide concentrates on a non-aqueous basis, which are sealed in a bag made of water-soluble plastic film.
Pesticides are normally marketed in the form of concentrates which, before use, are diluted with water to spray mixtures. When handling the concentrates, the toxicity of the active ingredients makes it necessary to take steps to prevent the user coming in contact with the concentrates. In particular, the user must be protected from inhaling the dust arising from handling solid formulations such as powders and granules, and from skin contact with liquid formulations such as emulsifiable concentrates. The manufacturers of pesticide concentrates therefore recommend taking a number of precautions, such as wearing protective masks, suits and gloves.
To secure further improved protection for the user, the proposal has already been made to avoid the dust formation associated with handling solid pesticide concentrates and skin contact with liquid concentrates by packaging these concentrates in a bag made from water-soluble plastic film. The spray mixture is prepared from such concentrates packed in water-soluble material by putting the concentrate and its packaging into the amount of water necessary for preparing the spray mixture. The spray mixture forms immediately after dissolution of the packaging and dispersion of the contents. Direct contact of the user with the concentrate is thereby avoided. Moreover, packaging concentrates in water-soluble packaging materials has the advantage that the concentrates can be removed from the containers in which they are transported and stored to protect them from moisture without leaving any residues which would make it necessary to clean the containers. In addition, it is much easier to control the dosage of the active ingredient, as each bag contains a defined amount of active ingredient.
The water-soluble bags of liquid active ingredient concentrates of the prior art have, however, a relatively high susceptibility to shock and impact, so that, when subjected to sudden mechanical stress, for example on falling to the ground, the bags burst. Not only do these unfavourable properties lead in the transportation and handling of such bags to -2constant loss and to contamination of the environment and/or of the user, but also to the loss of the advantages referred to above of the use of water-soluble packaging materials.
Hence it is the object of this invention to provide pesticide concentrates in packaged form which comprise a water-soluble packaging material and a liquid, non-aqueous pesticide concentrate, and which have increased stability to impact and shock.
Specifically, the invention provides pesticide concentrates in packaged form comprising a water-soluble packaging material and a liquid, non-aqueous pesticide concentrate, wherein the viscosity of said liquid pesticide concentrate is 1000-20 000 cp.
In the simplest case, the pesticide concentrates of this invention are solutions of one or more active ingredients in a non-aqueous solvent, the viscosity of which concentrates has been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance. The pesticide concentrates may also, however, be solutions of one or more active ingredients in a non-aqueous solvent, in which additionally one or more active ingredients which are insoluble in said solvent are suspended, the viscosity of which suspensions have also been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance. Finally, the concentrates of the invention may also be suspensions of one or more active ingredients in a non-aqueous solvent, the viscosity of which suspensions have been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance.
In addition to comprising one or more active ingredients, the solvent and the viscosity increasing substance, the concentrates of this invention may advantageously contain one or more dispersants. The addition of one or more dispersants is especially expedient if the active ingredient and/or the solvent and/or the viscosity increasing substance are insoluble in water and it is necessary to form a dispersion after diluting the concentrate with water.
Suitable non-aqueous solvents are the solvents which are customarily used in pesticide formulation and which are inert to the water-soluble packaging material, viz. those solvents which neither dissolve the water-soluble packaging material nor in which it swells or otherwise adversely affect it. With respect to this limitation, it must be borne in mind that solvents generally tend all the less to dissolve or cause the packaging material to swell the greater the concentration of the substances dissolved therein is. Suitable solvents are alcohols, alkanediols (glycols), diethylene glycol monoethers, ketones, esters, aliphatic and aromatic hydrocarbons, as well as mineral and vegetable oils. Particularly suitable -3alcohols are Cj-Cgalkanols, preferably C3-C6alkanols and C5-C6cycloalkanols. Particularly suitable alkanediols are ethylene glycol and propylene glycol. Particularly suitable diethylene glycol monoethers are diethylene glycol monomethyl ether und dipropylene glycol monomethyl ether. Particularly suitable ketones are C4-C8alkanones and C5-C6cycloalkanones. Suitable esters are preferably C3-C6alkylacetates and lactones of C4-C5hydroxyalkanecarboxylic acids. Particularly suitable aliphatic and aromatic hydrocarbons are hexane, cyclohexane, toluene, xylene, as well as mixtures of the alkylbenzenes which are commercially available under the registered trademarks ®Solvesso and ®Shellsol. Particularly suitable mineral oils are higher boiling petroleum fractions. Suitable vegetable oils are castor oil, rape oil, rape oil esters, cotton seed oil and soybean oil. Particularly suitable solvents are cyclohexanol, diacetone alcohol, cyclohexanone, butyrolactone, amyl acetate, toluene, xylene, as well as mixtures of alkylbenzenes having a boiling range of 130-170°C.
Suitable viscosity increasing substances for the putposes of the invention are preferably water-soluble polymers and hydrophilic silicic acid. Suitable water-soluble polymers are typically cellulose derivatives, proteins (gelatin) and polyvinylpyrrolidone having a molecular weight of 600 000-1000 000. In individual cases it is also possible to use surfactants, such as ethylene oxide-propylene oxide block polymers or dodecylbenzenesulfonates, as viscosity increasing substances. Preferred viscosity increasing substances are cellulose derivatives, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.
The dispersants which may be suitably used are basically all nonionic, anionic and cationic dispersants customarily used in the art of pesticide formulation. It is preferred to use nonionic or anionic dispersants or mixtures of nonionic and anionic dispersants. Particularly suitable nonionic dispersants are ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers, as well as fatty acid and fatty alcohol polyglycol ethers. Particularly suitable anionic dispersants are salts of alkylbenzenesulfonic acids, for example calcium dodecylbenzenesulfonate, and also salts of mono- and diphenol polyglycol ether phosphates, as well as salts of monophenol polyglycol ether sulfates. Particularly suitable mixtures of anionic and nonionic dispersants are mixtures of alkylphenol polyglycol ethers and salts of mono- and diphenol polyglycol ether phosphates.
By water-soluble packaging materials are meant in the context of this invention preferably -4films made of water-soluble polymers, for example of polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of vinyl alcohol and vinyl pyrrolidone, copolymers of vinyl alcohol and vinyl acetate, as well as cellulosic films, for example carboxymethyl cellulose films. Polyvinyl alcohol films are the preferred packaging materials.
The active ingredient concentrates of this invention may in principle contain any agrochemical control agents, for example insecticides, acaricides, fungicides, herbicides and plant growth regulating substances.
The pesticide concentrates of this invention can be prepared by dissolving or suspending one or more active ingredients in a solution of the dispersant in a non-aqueous solvent, and then incorporating the viscosity increasing substance in the resultant mixture. The preparation of the concentrates can be carried out in a conventional mixing apparatus. If the individual components of the mixture are water-soluble, the addition of dispersant can be dispensed with, for in this case an aqueous solution is obtained direct from the concentrate upon dilution with water. If, however, one or more components of the concentrate are water-insoluble, then it is advantageous to add one or more dispersants in order to ensure the rapid and homogeneous dispersion of the components in water. The concentrate can then be filled immediately in equal portions into bags which can be made in known manner from films consisting of the polymers cited above. After they have been filled with the concentrate, the bags are sealed. The bags so obtained contain a defined amount of active ingredient per unit dose package. The individual bags can then be packed for transportation and storage individually or collectively in containers, for example cardboard, polyethylene, polypropylene or polyvinyl chloride containers, from which they can be readily removed immediately before use.
The bags of this invention are conveniently prepared by continuously feeding a web of water-soluble material 100-300 mm wide and 30-40 pm thick to a filling machine in which the web is first welded with a straight bead to a tubular film which is sealed at its end by a transverse weld. After being filled with the desired amount of active ingredient concentrate, the bag is then sealed with a severing weld, so as to obtain, on the one hand, a ready-for-use bag containing the active ingredient concentrate and, on the other, a new bag preformed from the tubular film into which the next portion of active ingredient concentrate can be filled. The welds can be made by heat welding at a temperature of ca. 300°C as well as by pulse welding or high-frequency welding.
IE 9ΐ1θθ4 -5The handling and application of the pesticide concentrates of this invention is exceedingly simple. One or more bags are taken from the container and put into a spray tank filled with water in which the bag made of water-soluble packaging material dissolves in a few minutes, and the concentrate disperses in the water to form a spray mixture. Not only are the previously known advantages of water-soluble bags thereby attained, namely avoidance of direct contact of the user with the concentrate, ready metering of the active ingredients without using graduated jars, and avoidance of contamination of the packing containers, but, in addition, the mechanical stability of the bags, especially the stability to sudden mechanical stress, is substantially increased in comparison with prior art bags of this kind containing liquid pesticide concentrates. Only by increasing the stability to sudden mechanical stresses is it possible to utilise fully the advantages accruing from the use of water-soluble packaging material.
The following Examples illustrate the invention in more detail.
A number of typical formulations of pesticide concentrates of this invention are illustrated below, without thereby implying any restriction of the present invention. Percentages are by weight. The preparation of the packs is also described.
Example 1 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 4.5 % castor oil polyglycol ether (EO36) 4.0 % isooctylphenol polyglycol ether (EO 8) 2.0 % alkylbenzene C10-03, to make up 100 % viscosity: 11000 cp Example 2 Propiconazole techn. 65.0 % PO-EO block polymer (80 % EO; MG: 8550) 4.5 % castor oil polyglycol ether (EO 36) 8.8 % sodium diamylsulfosuccinate 4.6 % n-butanol, to make up viscosity: 5000 cp 100 % Example 3 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 3.0 % isotridecyl alcohol polyglycol ether (EO 6) 3.0 % EO-PO block polymer (20 % EO; MG: 5000) 4.0 % silicone oil 0.2 % hydroxypropyl cellulose 1.0 % cyclohexanone, to make up 100 % viscosity: 2000 cp Example 4 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 3.0 % isotridecyl alcohol polyglycol ether (EO 6) 3.0 % EO-PO block polymer (20 % EO; MG: 5000) 4.0 % silicone oil 0.2 % hydroxypropyl cellulose 1.0 % dipropylene glycol monomethyl ether, to make up 100 % viscosity: 2000 cp Example 5 Propiconazole techn. 62.5 % tristyrylphenol polyglycol ether (EO 20) 8.0 % nonylphenol polyglycol ether (EO8) 8.0 % nonylphenol polyglycol ether (EO 8-10) phosphate 2.0 % ¢911004 silicone oil 0.2 % hydroxypropylcellulose 0.72 % cyclohexanone, to make up viscosity: 2400 cp 100 % Example 6 Penconazole techn. 25.0 % propylene glycol isotridecyl alcohol polyglycol 7.0 % ether (EO 6) 3.0 % calcium dodecylbenzenesulfonate EO-PO block polymer 4.0 % (20 % EO; MG: 5000) 10.0 % silicone oil 0.05 % hydrophilic silicic acid 3.5 % castor oil, to make up viscosity: 5000 cp 100 % Example 7 Phosphamidon techn. 65.6 % calcium dodecylbenzenesulfonate 1.6 % polyglycerol phthalate oleyl alcohol polyglycol ether 1.6 % (10 EO) 3.0 % silicone oil 0.08 % hydroxypropyl cellulose dipropylene glycol monomethyl 0.82 % ester, to make up viscosity: 3000 cp 100 % Beispiel 8 Monocrotophos techn. 60.6 % hydroxypropylcellulose dipropylene glycol methyl ether, 4.0 % to make up viscosity: 3000 cp 100 % -8Example 9 propargyl 2- [4- (5-c h loro-5-fl uoropyrid-2-yloxy)phenoxy] - propioniate 24.0 % 5-chloro-8-( 1 -methylhexyloxycarbonylmethoxy)- quinoline 6.0 % N-methylpyrrolidone 5.0 % calcium dodecylbenzoate 7.0 % nonylphenol polypropylene( 13)polyethylene(20)- glycol 13.0 % hydrophilic silicic acid 2.1 % ethyl cellulose 2.1 % anisole, to make up 100 % viscosity: 2000 cp Example 10: A web of polyvinyl alcohol (manufacturer: Syntana Handelsgesellschaft GmbH, Millheim-Ruhr, FRG), 200 mm wide and 35 pm thick, is fed continuously to a filling machine (manufacturer: NEDI S.A., Saint-Mammes, France) in which it is welded by pulse welding with a straight bead to a tube which is sealed at its end with a transverse weld. After being filled with 100 g of active ingredient according to Example 3, the preformed bags so obtained are then separated so as to give sealed bags 135 mm in length which contain the active ingredient concentrate.
The bags so obtained dissolve in 25-2001 of water of 15-20°C in ca. 1 minute to give a ready-for-use spray mixture.
Claims (13)
1. A pesticide concentrate in packaged form, which comprises a water-soluble bag and a liquid, non-aqueous pesticide concentrate, the viscosity of said liquid pesticide concentrate being 1000-20 000 cp.
2. A pesticide concentrate according to claim 1, which contains one or more active ingredients selected from the group consisting of insecticides, acaricides, fungicides, herbicides and plant growth regulating substances.
3. A pesticide concentrate according to claim 1, which contains a solvent which is inert to the water-soluble packaging material.
4. A pesticide concentrate according to claim 3, which contains a solvent selected from the group consisting of alcohols, alkanediols (glycols), diethylene glycol monoethers, ketones, esters, aliphatic and aromatic hydrocarbons, and mineral or vegetable oils.
5. A pesticide concentrate according to claim 3, which contains a solvent selected from the group consisting of cyclohexanol, diacetone alcohol, cyclohexanone, butyrolactone, amyl acetate, toluene, xylene, and mixtures of alkylbenzenes having a boiling range of 130-170°C.
6. A pesticide concentrate according to claim 1, which contains one or more dispersants.
7. A pesticide concentrate according to claim 1, which contains a water-soluble polymer or hydrophilic silicic acid as viscosity increasing substance.
8. A pesticide concentrate according to claim 7, which contains a viscosity increasing substance selected from the group consisting of cellulose derivatives, proteins (gelatin) or polyvinyl pyrrolidine having a molecular weight of 600 000-1000 000.
9. A pesticide concentrate according to claim 8, which contains a viscosity increasing substance selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose. - 1010.
10.A pesticide concentrate according to claim 1, wherein the packaging material consists of a film made from a water-soluble polymer.
11. A pesticide concentrate according to claim 10, wherein the water-soluble packaging material is a film made from polyvinyl alcohol, polyvinyl pyrrolidone, a copolymer vinyl alcohol and vinyl pyrrolidone, a copolymer of vinyl alcohol and vinyl acetate, or is a cellulosic film.
12. A pesticide concentrate according to claim 10, wherein the packaging material is a polyvinyl alcohol film.
13. A pesticide concentrate according to any preceding claim, substantially as hereinbefore described and exemplified.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH101190 | 1990-03-27 |
Publications (2)
Publication Number | Publication Date |
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IE911004A1 true IE911004A1 (en) | 1991-10-09 |
IE66492B1 IE66492B1 (en) | 1996-01-10 |
Family
ID=4200366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE100491A IE66492B1 (en) | 1990-03-27 | 1991-03-26 | Liquid pesticide concentrates |
Country Status (15)
Country | Link |
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EP (1) | EP0449773B1 (en) |
KR (1) | KR0168059B1 (en) |
AT (1) | ATE121903T1 (en) |
AU (1) | AU646440B2 (en) |
BR (1) | BR9101192A (en) |
CA (1) | CA2039001C (en) |
CZ (1) | CZ284551B6 (en) |
DE (1) | DE59105355D1 (en) |
DK (1) | DK0449773T3 (en) |
ES (1) | ES2071963T3 (en) |
HU (1) | HU217519B (en) |
IE (1) | IE66492B1 (en) |
IL (1) | IL97669A (en) |
SK (1) | SK280182B6 (en) |
ZA (1) | ZA912257B (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5395616A (en) * | 1988-06-15 | 1995-03-07 | May & Baker Ltd. | Packaging for liquid products |
AU653519B2 (en) * | 1990-05-02 | 1994-10-06 | Rhone-Poulenc Agriculture Limited | Soluble sachets |
US5080226A (en) * | 1990-07-18 | 1992-01-14 | Rhone-Poulenc Ag Company | Containerization system for agrochemicals and the like |
IL98801A (en) * | 1990-07-18 | 1997-07-13 | Rhone Poulenc Agrochimie | Water dispersible gel formulations |
IL98803A (en) * | 1990-07-18 | 1996-06-18 | Rhone Poulenc Agrochimie | Gel formulations |
IL98805A0 (en) * | 1990-07-18 | 1992-07-15 | Rhone Poulenc Agrochimie | Gel formulations for hazardous products |
US5248038A (en) * | 1990-07-18 | 1993-09-28 | Rhone-Poulenc Inc. | Containerization system for agrochemicals and the like |
MA22221A1 (en) * | 1990-07-18 | 1992-04-01 | Rhone Poulenc Agrochimie | GEL FORMULATIONS FOR USE IN TOXIC PRODUCT PACKAGING SYSTEMS |
AU655282B2 (en) * | 1991-06-14 | 1994-12-15 | Rhone-Poulenc Agro | New aqueous formulations |
IL104187A (en) * | 1991-12-27 | 1996-05-14 | Rhone Poulenc Agrochimie | Containerization systems and composition suitable to be contained |
DE4417555A1 (en) * | 1994-05-19 | 1995-11-23 | Bayer Ag | Use of gel formulations as a mordant |
CN1108098C (en) | 1994-08-03 | 2003-05-14 | 曾尼卡有限公司 | Gel formulation |
DE19633271A1 (en) | 1996-08-19 | 1998-02-26 | Basf Ag | Liquid formulation of ethyl (Z) -2-chloro-3- [2-chloro-5- (4,5,6,7-tetrahydro-1,3-dioxoisoindoldion-2-yl) phenyl] acrylate |
AU3292299A (en) * | 1998-02-25 | 1999-09-15 | Uniroyal Chemical Company, Inc. | System and method for packaging a chemical composition |
US6727219B2 (en) | 2002-07-01 | 2004-04-27 | E. I. Du Pont De Nemours And Company | Single dosage oxidizing treatment |
CN114271272A (en) * | 2022-01-21 | 2022-04-05 | 李汉承 | Pesticide coagulated beads and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB922317A (en) * | 1958-05-05 | 1963-03-27 | Associated Fumigators Ltd | Improvements in or relating to means for packaging pesticides |
US3695989A (en) * | 1970-08-12 | 1972-10-03 | Robert E Albert | Cold water soluble foam plastic package |
IL90587A (en) * | 1988-06-15 | 1996-05-14 | May & Baker Ltd | Package releasing its contents on contact with water |
-
1991
- 1991-03-15 KR KR1019910004265A patent/KR0168059B1/en not_active IP Right Cessation
- 1991-03-19 AT AT91810176T patent/ATE121903T1/en not_active IP Right Cessation
- 1991-03-19 EP EP91810176A patent/EP0449773B1/en not_active Revoked
- 1991-03-19 DE DE59105355T patent/DE59105355D1/en not_active Revoked
- 1991-03-19 DK DK91810176.7T patent/DK0449773T3/en not_active Application Discontinuation
- 1991-03-19 ES ES91810176T patent/ES2071963T3/en not_active Expired - Lifetime
- 1991-03-25 IL IL9766991A patent/IL97669A/en not_active IP Right Cessation
- 1991-03-25 CA CA002039001A patent/CA2039001C/en not_active Expired - Fee Related
- 1991-03-26 CZ CS91809A patent/CZ284551B6/en not_active IP Right Cessation
- 1991-03-26 HU HU000/91A patent/HU217519B/en not_active IP Right Cessation
- 1991-03-26 AU AU73856/91A patent/AU646440B2/en not_active Ceased
- 1991-03-26 BR BR919101192A patent/BR9101192A/en not_active IP Right Cessation
- 1991-03-26 SK SK809-91A patent/SK280182B6/en unknown
- 1991-03-26 ZA ZA912257A patent/ZA912257B/en unknown
- 1991-03-26 IE IE100491A patent/IE66492B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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HUT56690A (en) | 1991-10-28 |
CZ284551B6 (en) | 1999-01-13 |
ES2071963T3 (en) | 1995-07-01 |
SK280182B6 (en) | 1999-09-10 |
IL97669A (en) | 1996-01-19 |
EP0449773A1 (en) | 1991-10-02 |
AU646440B2 (en) | 1994-02-24 |
KR0168059B1 (en) | 1999-01-15 |
CA2039001C (en) | 2001-04-24 |
KR910016250A (en) | 1991-11-05 |
ZA912257B (en) | 1991-12-24 |
EP0449773B1 (en) | 1995-05-03 |
DE59105355D1 (en) | 1995-06-08 |
ATE121903T1 (en) | 1995-05-15 |
DK0449773T3 (en) | 1995-07-17 |
IE66492B1 (en) | 1996-01-10 |
IL97669A0 (en) | 1992-06-21 |
BR9101192A (en) | 1991-11-05 |
CA2039001A1 (en) | 1991-09-28 |
CS9100809A2 (en) | 1991-11-12 |
HU217519B (en) | 2000-02-28 |
AU7385691A (en) | 1991-10-03 |
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