CA2375949A1 - Aqueous concentrate pesticidal compositions having improved dermal and ocular safety - Google Patents
Aqueous concentrate pesticidal compositions having improved dermal and ocular safety Download PDFInfo
- Publication number
- CA2375949A1 CA2375949A1 CA002375949A CA2375949A CA2375949A1 CA 2375949 A1 CA2375949 A1 CA 2375949A1 CA 002375949 A CA002375949 A CA 002375949A CA 2375949 A CA2375949 A CA 2375949A CA 2375949 A1 CA2375949 A1 CA 2375949A1
- Authority
- CA
- Canada
- Prior art keywords
- groups
- composition
- surfactant
- etheramine
- alkyl
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 239000012141 concentrate Substances 0.000 title claims abstract description 20
- 230000000361 pesticidal effect Effects 0.000 title claims abstract description 9
- 230000002500 effect on skin Effects 0.000 title description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 68
- -1 ether carboxylate Chemical class 0.000 claims abstract description 63
- 239000000575 pesticide Substances 0.000 claims abstract description 47
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 32
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 235000021317 phosphate Nutrition 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 24
- 239000005562 Glyphosate Substances 0.000 claims description 17
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 17
- 229940097068 glyphosate Drugs 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 239000004009 herbicide Substances 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- 230000002363 herbicidal effect Effects 0.000 claims description 7
- PVSGXWMWNRGTKE-UHFFFAOYSA-N 5-methyl-2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]pyridine-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC=C(C)C=C1C(O)=O PVSGXWMWNRGTKE-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 5
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 claims description 4
- LBGPXIPGGRQBJW-UHFFFAOYSA-N Difenzoquat Chemical compound C[N+]=1N(C)C(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 LBGPXIPGGRQBJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005630 Diquat Substances 0.000 claims description 4
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- RONFGUROBZGJKP-UHFFFAOYSA-N iminoctadine Chemical compound NC(N)=NCCCCCCCCNCCCCCCCCN=C(N)N RONFGUROBZGJKP-UHFFFAOYSA-N 0.000 claims description 4
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- KFEFNHNXZQYTEW-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-4-methylbenzoic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=CC(C)=CC=C1C(O)=O KFEFNHNXZQYTEW-UHFFFAOYSA-N 0.000 claims description 3
- NUPJIGQFXCQJBK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)-5-(methoxymethyl)nicotinic acid Chemical compound OC(=O)C1=CC(COC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 NUPJIGQFXCQJBK-UHFFFAOYSA-N 0.000 claims description 3
- CLQMBPJKHLGMQK-UHFFFAOYSA-N 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC=CC=C1C(O)=O CLQMBPJKHLGMQK-UHFFFAOYSA-N 0.000 claims description 3
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005561 Glufosinate Substances 0.000 claims description 3
- 239000005566 Imazamox Substances 0.000 claims description 3
- 239000005981 Imazaquin Substances 0.000 claims description 3
- XVOKUMIPKHGGTN-UHFFFAOYSA-N Imazethapyr Chemical compound OC(=O)C1=CC(CC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 XVOKUMIPKHGGTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- QZXCCPZJCKEPSA-UHFFFAOYSA-N chlorfenac Chemical compound OC(=O)CC1=C(Cl)C=CC(Cl)=C1Cl QZXCCPZJCKEPSA-UHFFFAOYSA-N 0.000 claims description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 claims description 2
- GXEKYRXVRROBEV-FBXFSONDSA-N (1r,2s,3r,4s)-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1C[C@@H]2[C@@H](C(O)=O)[C@@H](C(=O)O)[C@H]1O2 GXEKYRXVRROBEV-FBXFSONDSA-N 0.000 claims description 2
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 claims description 2
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 claims description 2
- XZIDTOHMJBOSOX-UHFFFAOYSA-N 2,3,6-TBA Chemical compound OC(=O)C1=C(Cl)C=CC(Cl)=C1Cl XZIDTOHMJBOSOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002794 2,4-DB Substances 0.000 claims description 2
- YIVXMZJTEQBPQO-UHFFFAOYSA-N 2,4-DB Chemical compound OC(=O)CCCOC1=CC=C(Cl)C=C1Cl YIVXMZJTEQBPQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims description 2
- MZHCENGPTKEIGP-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1Cl MZHCENGPTKEIGP-UHFFFAOYSA-N 0.000 claims description 2
- WNTGYJSOUMFZEP-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1C WNTGYJSOUMFZEP-UHFFFAOYSA-N 0.000 claims description 2
- GOCUAJYOYBLQRH-UHFFFAOYSA-N 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl GOCUAJYOYBLQRH-UHFFFAOYSA-N 0.000 claims description 2
- YUVKUEAFAVKILW-UHFFFAOYSA-N 2-(4-{[5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 YUVKUEAFAVKILW-UHFFFAOYSA-N 0.000 claims description 2
- OOLBCHYXZDXLDS-UHFFFAOYSA-N 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CC=C(Cl)C=C1Cl OOLBCHYXZDXLDS-UHFFFAOYSA-N 0.000 claims description 2
- MPPOHAUSNPTFAJ-UHFFFAOYSA-N 2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 MPPOHAUSNPTFAJ-UHFFFAOYSA-N 0.000 claims description 2
- ZJRUTGDCLVIVRD-UHFFFAOYSA-N 2-[4-chloro-2-(hydroxymethyl)phenoxy]acetic acid Chemical compound OCC1=CC(Cl)=CC=C1OCC(O)=O ZJRUTGDCLVIVRD-UHFFFAOYSA-N 0.000 claims description 2
- LLWADFLAOKUBDR-UHFFFAOYSA-N 2-methyl-4-chlorophenoxybutyric acid Chemical compound CC1=CC(Cl)=CC=C1OCCCC(O)=O LLWADFLAOKUBDR-UHFFFAOYSA-N 0.000 claims description 2
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims description 2
- CTSLUCNDVMMDHG-UHFFFAOYSA-N 5-bromo-3-(butan-2-yl)-6-methylpyrimidine-2,4(1H,3H)-dione Chemical compound CCC(C)N1C(=O)NC(C)=C(Br)C1=O CTSLUCNDVMMDHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005489 Bromoxynil Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- HSSBORCLYSCBJR-UHFFFAOYSA-N Chloramben Chemical compound NC1=CC(Cl)=CC(C(O)=O)=C1Cl HSSBORCLYSCBJR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005974 Chlormequat Substances 0.000 claims description 2
- IVHVNMLJNASKHW-UHFFFAOYSA-M Chlorphonium chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=C(Cl)C=C1Cl IVHVNMLJNASKHW-UHFFFAOYSA-M 0.000 claims description 2
- 239000005500 Clopyralid Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- NDUPDOJHUQKPAG-UHFFFAOYSA-N Dalapon Chemical compound CC(Cl)(Cl)C(O)=O NDUPDOJHUQKPAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005975 Daminozide Substances 0.000 claims description 2
- NOQGZXFMHARMLW-UHFFFAOYSA-N Daminozide Chemical compound CN(C)NC(=O)CCC(O)=O NOQGZXFMHARMLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005504 Dicamba Substances 0.000 claims description 2
- 239000005506 Diclofop Substances 0.000 claims description 2
- 239000005976 Ethephon Substances 0.000 claims description 2
- YQVMVCCFZCMYQB-UHFFFAOYSA-N Flamprop Chemical compound C=1C=C(F)C(Cl)=CC=1N(C(C)C(O)=O)C(=O)C1=CC=CC=C1 YQVMVCCFZCMYQB-UHFFFAOYSA-N 0.000 claims description 2
- DHAHEVIQIYRFRG-UHFFFAOYSA-N Fluoroglycofen Chemical compound C1=C([N+]([O-])=O)C(C(=O)OCC(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 DHAHEVIQIYRFRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005948 Formetanate Substances 0.000 claims description 2
- 239000005790 Fosetyl Substances 0.000 claims description 2
- 239000005574 MCPA Substances 0.000 claims description 2
- 239000005575 MCPB Substances 0.000 claims description 2
- 101150039283 MCPB gene Proteins 0.000 claims description 2
- 239000005984 Mepiquat Substances 0.000 claims description 2
- 239000002169 Metam Substances 0.000 claims description 2
- 239000005916 Methomyl Substances 0.000 claims description 2
- 239000005950 Oxamyl Substances 0.000 claims description 2
- YYVFXSYQSOZCOQ-UHFFFAOYSA-N Oxyquinoline sulfate Chemical compound [O-]S([O-])(=O)=O.C1=C[NH+]=C2C(O)=CC=CC2=C1.C1=C[NH+]=C2C(O)=CC=CC2=C1 YYVFXSYQSOZCOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005595 Picloram Substances 0.000 claims description 2
- 229930182764 Polyoxin Natural products 0.000 claims description 2
- 239000005821 Propamocarb Substances 0.000 claims description 2
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005627 Triclopyr Substances 0.000 claims description 2
- 229930195482 Validamycin Natural products 0.000 claims description 2
- CTJBHIROCMPUKL-WEVVVXLNSA-N [(e)-3-methylsulfonylbutan-2-ylideneamino] n-methylcarbamate Chemical compound CNC(=O)O\N=C(/C)C(C)S(C)(=O)=O CTJBHIROCMPUKL-WEVVVXLNSA-N 0.000 claims description 2
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 claims description 2
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- VGPYEHKOIGNJKV-UHFFFAOYSA-N asulam Chemical compound COC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 VGPYEHKOIGNJKV-UHFFFAOYSA-N 0.000 claims description 2
- OTSAMNSACVKIOJ-UHFFFAOYSA-N azane;carbamoyl(ethoxy)phosphinic acid Chemical compound [NH4+].CCOP([O-])(=O)C(N)=O OTSAMNSACVKIOJ-UHFFFAOYSA-N 0.000 claims description 2
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 claims description 2
- GINJFDRNADDBIN-FXQIFTODSA-N bilanafos Chemical compound OC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@@H](N)CCP(C)(O)=O GINJFDRNADDBIN-FXQIFTODSA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 claims description 2
- JUZXDNPBRPUIOR-UHFFFAOYSA-N chlormequat Chemical compound C[N+](C)(C)CCCl JUZXDNPBRPUIOR-UHFFFAOYSA-N 0.000 claims description 2
- PIZCXVUFSNPNON-UHFFFAOYSA-N clofencet Chemical compound CCC1=C(C(O)=O)C(=O)C=NN1C1=CC=C(Cl)C=C1 PIZCXVUFSNPNON-UHFFFAOYSA-N 0.000 claims description 2
- HUBANNPOLNYSAD-UHFFFAOYSA-N clopyralid Chemical compound OC(=O)C1=NC(Cl)=CC=C1Cl HUBANNPOLNYSAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 claims description 2
- VEENJGZXVHKXNB-VOTSOKGWSA-N dicrotophos Chemical compound COP(=O)(OC)O\C(C)=C\C(=O)N(C)C VEENJGZXVHKXNB-VOTSOKGWSA-N 0.000 claims description 2
- FWCBATIDXGJRMF-UHFFFAOYSA-N dikegulac Natural products C12OC(C)(C)OCC2OC2(C(O)=O)C1OC(C)(C)O2 FWCBATIDXGJRMF-UHFFFAOYSA-N 0.000 claims description 2
- BGZZWXTVIYUUEY-UHFFFAOYSA-N fomesafen Chemical compound C1=C([N+]([O-])=O)C(C(=O)NS(=O)(=O)C)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 BGZZWXTVIYUUEY-UHFFFAOYSA-N 0.000 claims description 2
- RMFNNCGOSPBBAD-MDWZMJQESA-N formetanate Chemical compound CNC(=O)OC1=CC=CC(\N=C\N(C)C)=C1 RMFNNCGOSPBBAD-MDWZMJQESA-N 0.000 claims description 2
- VUERQRKTYBIULR-UHFFFAOYSA-N fosetyl Chemical compound CCOP(O)=O VUERQRKTYBIULR-UHFFFAOYSA-N 0.000 claims description 2
- NRXQIUSYPAHGNM-UHFFFAOYSA-N ioxynil Chemical compound OC1=C(I)C=C(C#N)C=C1I NRXQIUSYPAHGNM-UHFFFAOYSA-N 0.000 claims description 2
- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 claims description 2
- NNCAWEWCFVZOGF-UHFFFAOYSA-N mepiquat Chemical compound C[N+]1(C)CCCCC1 NNCAWEWCFVZOGF-UHFFFAOYSA-N 0.000 claims description 2
- 229960002523 mercuric chloride Drugs 0.000 claims description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 2
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 claims description 2
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims description 2
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 claims description 2
- GEPDYQSQVLXLEU-AATRIKPKSA-N methyl (e)-3-dimethoxyphosphoryloxybut-2-enoate Chemical compound COC(=O)\C=C(/C)OP(=O)(OC)OC GEPDYQSQVLXLEU-AATRIKPKSA-N 0.000 claims description 2
- 229960002939 metizoline Drugs 0.000 claims description 2
- 229960001952 metrifonate Drugs 0.000 claims description 2
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- UQJQVUOTMVCFHX-UHFFFAOYSA-L nabam Chemical compound [Na+].[Na+].[S-]C(=S)NCCNC([S-])=S UQJQVUOTMVCFHX-UHFFFAOYSA-L 0.000 claims description 2
- JXTHEWSKYLZVJC-UHFFFAOYSA-N naptalam Chemical compound OC(=O)C1=CC=CC=C1C(=O)NC1=CC=CC2=CC=CC=C12 JXTHEWSKYLZVJC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002715 nicotine Drugs 0.000 claims description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 claims description 2
- 229940079888 nitenpyram Drugs 0.000 claims description 2
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 claims description 2
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical compound CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 claims description 2
- PMCVMORKVPSKHZ-UHFFFAOYSA-N oxydemeton-methyl Chemical compound CCS(=O)CCSP(=O)(OC)OC PMCVMORKVPSKHZ-UHFFFAOYSA-N 0.000 claims description 2
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 claims description 2
- NQQVFXUMIDALNH-UHFFFAOYSA-N picloram Chemical compound NC1=C(Cl)C(Cl)=NC(C(O)=O)=C1Cl NQQVFXUMIDALNH-UHFFFAOYSA-N 0.000 claims description 2
- YEBIHIICWDDQOL-YBHNRIQQSA-N polyoxin Polymers O[C@@H]1[C@H](O)[C@@H](C(C=O)N)O[C@H]1N1C(=O)NC(=O)C(C(O)=O)=C1 YEBIHIICWDDQOL-YBHNRIQQSA-N 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- WZZLDXDUQPOXNW-UHFFFAOYSA-N propamocarb Chemical compound CCCOC(=O)NCCCN(C)C WZZLDXDUQPOXNW-UHFFFAOYSA-N 0.000 claims description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 claims description 2
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 claims description 2
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 claims description 2
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 claims description 2
- LESVOLZBIFDZGS-UHFFFAOYSA-N vamidothion Chemical compound CNC(=O)C(C)SCCSP(=O)(OC)OC LESVOLZBIFDZGS-UHFFFAOYSA-N 0.000 claims description 2
- NDNKHWUXXOFHTD-UHFFFAOYSA-N metizoline Chemical compound CC=1SC2=CC=CC=C2C=1CC1=NCCN1 NDNKHWUXXOFHTD-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- DEWVPZYHFVYXMZ-QCILGFJPSA-M sodium;(3ar,4as,8ar,8bs)-2,2,7,7-tetramethyl-4a,5,8a,8b-tetrahydro-[1,3]dioxolo[3,4]furo[1,3-d][1,3]dioxine-3a-carboxylate Chemical compound [Na+].O([C@H]12)C(C)(C)OC[C@@H]1O[C@]1(C([O-])=O)[C@H]2OC(C)(C)O1 DEWVPZYHFVYXMZ-QCILGFJPSA-M 0.000 claims 1
- 235000008504 concentrate Nutrition 0.000 description 16
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- 206010015946 Eye irritation Diseases 0.000 description 12
- 231100000013 eye irritation Toxicity 0.000 description 12
- 206010070835 Skin sensitisation Diseases 0.000 description 8
- 231100000370 skin sensitisation Toxicity 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 206010040880 Skin irritation Diseases 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 210000000795 conjunctiva Anatomy 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000005648 plant growth regulator Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 231100000635 Draize test Toxicity 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 231100000493 OECD 406 (Buehler) Skin Sensitisation Toxicity 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 239000002085 irritant Substances 0.000 description 3
- 231100000021 irritant Toxicity 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000004550 soluble concentrate Substances 0.000 description 3
- 239000004546 suspension concentrate Substances 0.000 description 3
- UUIPAJHTKDSSOK-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)(O)=O UUIPAJHTKDSSOK-UHFFFAOYSA-N 0.000 description 2
- 241000700198 Cavia Species 0.000 description 2
- 206010010726 Conjunctival oedema Diseases 0.000 description 2
- 208000006069 Corneal Opacity Diseases 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
- 230000000895 acaricidal effect Effects 0.000 description 2
- 239000000642 acaricide Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 231100000269 corneal opacity Toxicity 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 description 2
- 230000000266 injurious effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005645 nematicide Substances 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical class O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FWCBATIDXGJRMF-FLNNQWSLSA-N Dikegulac Chemical compound O([C@H]12)C(C)(C)OC[C@@H]1O[C@]1(C(O)=O)[C@H]2OC(C)(C)O1 FWCBATIDXGJRMF-FLNNQWSLSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 241001233242 Lontra Species 0.000 description 1
- 208000021957 Ocular injury Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- HYJSGOXICXYZGS-UHFFFAOYSA-N benazolin Chemical compound C1=CC=C2SC(=O)N(CC(=O)O)C2=C1Cl HYJSGOXICXYZGS-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000003503 early effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 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
- 239000003337 fertilizer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-O isopropylaminium Chemical compound CC(C)[NH3+] JJWLVOIRVHMVIS-UHFFFAOYSA-O 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 125000005644 linolenyl group Chemical group 0.000 description 1
- 125000005645 linoleyl group Chemical group 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011587 new zealand white rabbit Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004548 suspo-emulsion Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000003442 weekly effect Effects 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
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An aqueous concentrate pesticidal composition is provided, comprising (a) a water-soluble pesticide in an amount of about 50 to about 500 g/l; (b) an etheramine surfactant; and (c) an anionic surfactant having the chemical formula (III) R7-(O-R8)n-O-X where R7 is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R8 groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate; the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1. Compositions of the invention have reduced injuriousness to skin and/or eyes than otherwise similar compositions lacking only the anionic surfactant.
Description
AQUEOUS CONCENTRATE PESTICIDAL COMPOSITIONS HAVING IMPROVED
DERMAL AND OCULAR SAFETY
FIELD OF THE INVENTION
The present invention relates to aqueous concentrate formulations containing a water-s soluble pesticide or plant growth regulator useful in agriculture and other situations. Hereinafter the term "pesticide" is used for brevity to include plant growth regulators.
The present invention more particularly relates to such formulations further containing a surfactant of the etheramine class that enhances efficacy of the pesticide but that imparts to the aqueous concentrate an undesirable degree of injuriousness in the event of accidental contact with the skin and/or eyes of io a person handling the aqueous concentrate. The present invention reduces or overcomes such injuriousness while at least maintaining the high degree of efficacy imparted to the pesticide by the etheramine surfactant.
BACKGROUND OF THE INVENTION
Water-soluble pesticides, including without restriction herbicides, fungicides, is insecticides, acaricides, nematicides and plant growth regulators, are conveniently formulated as aqueous concentrates, wherein the pesticidal active ingredient is present in concentrated aqueous solution. A "concentrate" herein is a composition having an active ingredient concentration greater than about 50 g/1, up to the limit of solubility of the active ingredient in water; where the active ingredient is a salt of a pesticidally active acid, the lower limit of about 50 g/1 is to be Zo understood to relate to the concentration of the active ingredient expressed as acid equivalent (a.e.). An "aqueous concentrate" herein is a liquid concentrate having a single phase that is an aqueous solution of the pesticide, or having a continuous phase that is an aqueous solution of the pesticide and one or more discontinuous phases that are other than aqueous, e.g., an oil-in-water emulsion, an aqueous suspension concentrate or a suspoemulsion. Aqueous concentrates are Zs diluted in a suitable volume of water by the end-user and the resulting diluted composition is applied most commonly by spraying.
Particularly where the pesticide is to be applied to foliage of plants such as crops or weeds, it is common for the aqueous concentrate to contain one or more surfactants. Surfactants assist in retention on the foliage of droplets of the applied spray, adhesion of the spray droplets to 3o the foliar surface and penetration of the water-soluble pesticide through the hydrophobic cuticle that covers the foliar surface, by these means and possibly in otter ways enhancing biological effectiveness of the pesticide. A particularly useful class of surfactants providing enhanced biological effectiveness is described herein by the generic term "etheramine".
Compositions of certain etheramine surfactants with the herbicide glyphosate or its salts are disclosed in U.S.
s Patent No. 5,750,468 to Wright.
Etheramine surfactants are compounds having, when present in an aqueous medium at a pH of about 4, the chemical formula (I) (R3_O)x_R4 R~_~O_R2 N+_Rs At_ )m ~ t v ~Rs_~)y R4 where Rl is a C6_22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 io and R3 groups are independently C2_4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C~_4 alkyl or benzyl groups, Rs is hydrogen, a C1~
alkyl or benzyl group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1_4 alkylidene, t is 1 or 2, A'- is a suitable anion, and v is 1 except where Rs is an anionic moiety in is which case v is 0.
Etheramine surfactants of formula (I) above in which Rs is hydrogen are herein generally referred to as "tertiary etheramines" (an exception is where x and y are 0 and each R4 group is hydrogen, giving a primary etheramine). At some pH level higher than 4, for example at a pH of about 8, the nitrogen atom of such a tertiary etheramine is typically non-protonated and the zo tertiary etheramine, having no anion At- associated with it, can be described by the chemical formula (II) (Ra-~)X R4 R~-O-R2)m ~R3-~)y R4 where Rl, RZ, R3, R4, m, x and y are as defined for formula (I) above.
DERMAL AND OCULAR SAFETY
FIELD OF THE INVENTION
The present invention relates to aqueous concentrate formulations containing a water-s soluble pesticide or plant growth regulator useful in agriculture and other situations. Hereinafter the term "pesticide" is used for brevity to include plant growth regulators.
The present invention more particularly relates to such formulations further containing a surfactant of the etheramine class that enhances efficacy of the pesticide but that imparts to the aqueous concentrate an undesirable degree of injuriousness in the event of accidental contact with the skin and/or eyes of io a person handling the aqueous concentrate. The present invention reduces or overcomes such injuriousness while at least maintaining the high degree of efficacy imparted to the pesticide by the etheramine surfactant.
BACKGROUND OF THE INVENTION
Water-soluble pesticides, including without restriction herbicides, fungicides, is insecticides, acaricides, nematicides and plant growth regulators, are conveniently formulated as aqueous concentrates, wherein the pesticidal active ingredient is present in concentrated aqueous solution. A "concentrate" herein is a composition having an active ingredient concentration greater than about 50 g/1, up to the limit of solubility of the active ingredient in water; where the active ingredient is a salt of a pesticidally active acid, the lower limit of about 50 g/1 is to be Zo understood to relate to the concentration of the active ingredient expressed as acid equivalent (a.e.). An "aqueous concentrate" herein is a liquid concentrate having a single phase that is an aqueous solution of the pesticide, or having a continuous phase that is an aqueous solution of the pesticide and one or more discontinuous phases that are other than aqueous, e.g., an oil-in-water emulsion, an aqueous suspension concentrate or a suspoemulsion. Aqueous concentrates are Zs diluted in a suitable volume of water by the end-user and the resulting diluted composition is applied most commonly by spraying.
Particularly where the pesticide is to be applied to foliage of plants such as crops or weeds, it is common for the aqueous concentrate to contain one or more surfactants. Surfactants assist in retention on the foliage of droplets of the applied spray, adhesion of the spray droplets to 3o the foliar surface and penetration of the water-soluble pesticide through the hydrophobic cuticle that covers the foliar surface, by these means and possibly in otter ways enhancing biological effectiveness of the pesticide. A particularly useful class of surfactants providing enhanced biological effectiveness is described herein by the generic term "etheramine".
Compositions of certain etheramine surfactants with the herbicide glyphosate or its salts are disclosed in U.S.
s Patent No. 5,750,468 to Wright.
Etheramine surfactants are compounds having, when present in an aqueous medium at a pH of about 4, the chemical formula (I) (R3_O)x_R4 R~_~O_R2 N+_Rs At_ )m ~ t v ~Rs_~)y R4 where Rl is a C6_22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 io and R3 groups are independently C2_4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C~_4 alkyl or benzyl groups, Rs is hydrogen, a C1~
alkyl or benzyl group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1_4 alkylidene, t is 1 or 2, A'- is a suitable anion, and v is 1 except where Rs is an anionic moiety in is which case v is 0.
Etheramine surfactants of formula (I) above in which Rs is hydrogen are herein generally referred to as "tertiary etheramines" (an exception is where x and y are 0 and each R4 group is hydrogen, giving a primary etheramine). At some pH level higher than 4, for example at a pH of about 8, the nitrogen atom of such a tertiary etheramine is typically non-protonated and the zo tertiary etheramine, having no anion At- associated with it, can be described by the chemical formula (II) (Ra-~)X R4 R~-O-R2)m ~R3-~)y R4 where Rl, RZ, R3, R4, m, x and y are as defined for formula (I) above.
Etheramine surfactants of formula (I) above in which R5 is a C1_4 alkyl or benzyl group are herein generally referred to as "quaternary etheramines" (an exception is where x and y are 0 and each R4 group is hydrogen, giving a secondary etheramine). Etheramine surfactants of formula (I) above in which RS is an anionic moiety and v is 0 are herein generally referred to as s "amphoteric etheramines" and include "etheramine oxides" (where RS is -O-) and "etherbetaines" (where RS is -CH2-COO-).
Many surfactants having amine functions, when present in an aqueous concentrate pesticide composition at concentrations giving useful enhancement of pesticidal efficacy, unfortunately impart to the composition an undesirable degree of injuriousness in the event of Io accidental contact with the skin and/or eyes of a person handling the composition. Regulations governing pesticide labelling in the United States and a number of other countries are such that injuriousness to skin and/or eyes due to presence of a surfactant in a pesticide formulation can result in restrictions on the use of such a formulation.
U.S. Patent No. 5,703,015 to Berger et al. ("the '015 patent") discloses that eye irritancy is of an aqueous concentrate pesticide composition due to presence therein of a polyoxyalkylene alkylamine surfactant can be reduced by inclusion in the composition of an acidic surfactant having a Cg_2o alkyl or alkylphenyl group. Specific classes of acidic surfactants disclosed to be useful are polyoxyalkylene alkylphenol sulfates, alcohol sulfates, polyoxyalkylene alcohol sulfates, mono- and dialcohol phosphates, mono- and di(polyoxyalkylene alcohol) phosphates, ao mono- and di(polyoxyalkylene alkylphenol) phosphates, polyoxyalkylene alkylphenol carboxylates and polyoxyalkylene alcohol carboxylates. The amount of acidic surfactant relative to the amount of polyoxyalkylene alkylamine surfactant appeared to have a strong bearing on the degree of eye irritancy reduction. For example, at a weight ratio of polyoxyethylene (4) nonylphenol phosphate to polyoxyethylene (16-17) tallowamine of about 1:5.5 (Example 20 of zs the '015 patent) eye irritation remained at a relatively high level up to 21 days after exposure, whereas with the same total surfactant concentration but at a weight ratio of polyoxyethylene (4) nonylphenol phosphate to polyoxyethylene (16-17) tallowamine of about 1:1.5 (Example 26 of the '015 patent) eye irritation had fallen to a low level by 7 days after exposure.
Many surfactants having amine functions, when present in an aqueous concentrate pesticide composition at concentrations giving useful enhancement of pesticidal efficacy, unfortunately impart to the composition an undesirable degree of injuriousness in the event of Io accidental contact with the skin and/or eyes of a person handling the composition. Regulations governing pesticide labelling in the United States and a number of other countries are such that injuriousness to skin and/or eyes due to presence of a surfactant in a pesticide formulation can result in restrictions on the use of such a formulation.
U.S. Patent No. 5,703,015 to Berger et al. ("the '015 patent") discloses that eye irritancy is of an aqueous concentrate pesticide composition due to presence therein of a polyoxyalkylene alkylamine surfactant can be reduced by inclusion in the composition of an acidic surfactant having a Cg_2o alkyl or alkylphenyl group. Specific classes of acidic surfactants disclosed to be useful are polyoxyalkylene alkylphenol sulfates, alcohol sulfates, polyoxyalkylene alcohol sulfates, mono- and dialcohol phosphates, mono- and di(polyoxyalkylene alcohol) phosphates, ao mono- and di(polyoxyalkylene alkylphenol) phosphates, polyoxyalkylene alkylphenol carboxylates and polyoxyalkylene alcohol carboxylates. The amount of acidic surfactant relative to the amount of polyoxyalkylene alkylamine surfactant appeared to have a strong bearing on the degree of eye irritancy reduction. For example, at a weight ratio of polyoxyethylene (4) nonylphenol phosphate to polyoxyethylene (16-17) tallowamine of about 1:5.5 (Example 20 of zs the '015 patent) eye irritation remained at a relatively high level up to 21 days after exposure, whereas with the same total surfactant concentration but at a weight ratio of polyoxyethylene (4) nonylphenol phosphate to polyoxyethylene (16-17) tallowamine of about 1:1.5 (Example 26 of the '015 patent) eye irritation had fallen to a low level by 7 days after exposure.
U.S. Patent No. 5,389,598 to Berk et al. discloses that alkyl mono- and dicarboxylic acids are also effective in reducing eye irritancy of pesticide compositions containing a polyoxyalkylene alkylamine surfactant.
SUMMARY OF THE INVENTION
s It has now been found that certain etheramine surfactants can impart to an aqueous concentrate composition comprising a water-soluble pesticide an undesirable level of injuriousness to skin and/or eyes. This injuriousness can take the form of one or more of several adverse effects, including eye irritation, skin irritation and skin sensitization.
There is now provided a solution to the problem of such injuriousness to skin and/or io eyes. According to the present invention, an aqueous concentrate pesticidal composition is provided, comprising (a) a water-soluble pesticide in an amount of about 50 to about 500 g/1; (b) an etheramine surfactant of formula (I) in an amount sufficient, if it were the sole surfactant present, to increase the level of injuriousness of the composition to skin and/or eyes; and (c) an anionic surfactant having the chemical formula (III) is R'-(O-R8)~ O-X
where R~ is a C4_22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8_12 alkyl)phenyl group, Rg groups are independently C2_4 alkylidene groups, n is 0 to about 60 and X
is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate; the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1.
2o Also provided is a method of reducing the injuriousness to skin and/or eyes of an aqueous concentrate pesticidal composition that comprises (a) a water-soluble pesticide in an amount of about 50 to about 600 g/1, and (b) an etheramine surfactant of formula (I);
said method comprising addition to the composition of an anionic surfactant of formula (III) in a weight ratio of the anionic surfactant to the etheramine surfactant of about 1:10 to about 1:1.
Zs In a preferred embodiment of the invention the etheramine surfactant is a tertiary etheramine of formula (II).
In a particularly preferred embodiment of the invention the anionic surfactant is a mono(polyoxyethylene alkyl or alkylphenyl ether) phosphate, alternatively described as a phosphate mono(polyoxyethylene alkyl or alkylphenyl) ester, optionally accompanied by the 3o corresponding phosphate diester.
SUMMARY OF THE INVENTION
s It has now been found that certain etheramine surfactants can impart to an aqueous concentrate composition comprising a water-soluble pesticide an undesirable level of injuriousness to skin and/or eyes. This injuriousness can take the form of one or more of several adverse effects, including eye irritation, skin irritation and skin sensitization.
There is now provided a solution to the problem of such injuriousness to skin and/or io eyes. According to the present invention, an aqueous concentrate pesticidal composition is provided, comprising (a) a water-soluble pesticide in an amount of about 50 to about 500 g/1; (b) an etheramine surfactant of formula (I) in an amount sufficient, if it were the sole surfactant present, to increase the level of injuriousness of the composition to skin and/or eyes; and (c) an anionic surfactant having the chemical formula (III) is R'-(O-R8)~ O-X
where R~ is a C4_22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8_12 alkyl)phenyl group, Rg groups are independently C2_4 alkylidene groups, n is 0 to about 60 and X
is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate; the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1.
2o Also provided is a method of reducing the injuriousness to skin and/or eyes of an aqueous concentrate pesticidal composition that comprises (a) a water-soluble pesticide in an amount of about 50 to about 600 g/1, and (b) an etheramine surfactant of formula (I);
said method comprising addition to the composition of an anionic surfactant of formula (III) in a weight ratio of the anionic surfactant to the etheramine surfactant of about 1:10 to about 1:1.
Zs In a preferred embodiment of the invention the etheramine surfactant is a tertiary etheramine of formula (II).
In a particularly preferred embodiment of the invention the anionic surfactant is a mono(polyoxyethylene alkyl or alkylphenyl ether) phosphate, alternatively described as a phosphate mono(polyoxyethylene alkyl or alkylphenyl) ester, optionally accompanied by the 3o corresponding phosphate diester.
A composition of the invention exhibits a lower degree of eye irritation, skin irritation and/or skin sensitization than a corresponding composition having the same total surfactant concentration but having none of the anionic surfactant. A preferred composition of the invention exhibits a lower degree of eye irritation, skin irritation and/or skin sensitization than a s corresponding composition having the same concentration of the etheramine surfactant but wherein the anionic surfactant is replaced entirely with water. The invention has been found to be of particular utility where the water-soluble pesticide is a salt of the herbicide glyphosate.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to aqueous concentrate compositions, including io formulations known in the art as soluble concentrates (SL), oil-in-water emulsions (EW), water-based suspension concentrates (SC) and suspoemulsions (SE). In all cases a water-soluble pesticide is present in solution in an aqueous phase of the composition. The concentration of the water-soluble pesticide is expressed herein on an active ingredient (a.i.) basis except where the active ingredient is a salt of a biologically active acid, in which case the concentration is is expressed on an acid equivalent (a.e.) basis. The concentration of pesticide (a.i. or a.e. as appropriate) in the composition as a whole ranges from about 50 to about 600 g/1; preferred compositions have a pesticide concentration of about 360 to about 540 g/1.
A "water-soluble" pesticide herein, including a salt or other water-soluble derivative of a pesticide, is one having a solubility in deionized water at 20°C of not less than about 50 g/1, more ao preferably not less than about 200 g/1.
Water-soluble fungicides and bactericides useful in compositions of the invention illustratively include borax, sec-butylamine, calcium polysulfide, copper sulfate, fosetyl, guazatine, hydroxyquinoline sulfate, iminoctadine, kasugamycin, mercuric chloride, metam, nabam, polyoxin B, propamocarb and validamycin and/or water-soluble salts thereof. Water-Zs soluble insecticides, acaricides and nematicides useful in compositions of the invention illustratively include acephate, butoxycarboxim, cartap, dicrotophos, formetanate, hydrogen cyanide, methamidophos, methomyl, mevinphos, monocrotophos, nicotine, nitenpyram, omethoate, oxamyl, oxydemeton-methyl, phosphamidon, thiocyclam, trichlorfon and vamidothion and/or water-soluble salts thereof. Water-soluble plant growth regulators useful in 3o compositions of the invention illustratively include chlormequat, chlorphonium, clofencet, cloxyfonac, cyanamide, daminozide, dikegulac, ethephon and mepiquat and/or water-soluble salts thereof.
In one embodiment of the invention, the water-soluble pesticide is a herbicide or an agriculturally acceptable salt thereof, including without restriction salts of acifluorfen, asulam, s benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, fluazifop, fluoroglycofen, fomesafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, io sulfamic acid, 2,3,6-TBA, TCA and triclopyr.
Preferred water-soluble herbicides are salts of acid compounds whose molecular structure comprises at least one of each of amine, carboxylate, and either phosphonate or phosphinate functional groups. This category includes salts of the herbicides N-phosphonomethylglycine (glyphosate) and DL-homoalanin-4-yl(methyl)phosphinate (glufosinate). Another preferred is group of herbicides are salts of compounds of the imidazolinone class, including imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin and imazethapyr.
Where the herbicide is cationic or forms canons in the presence of an acid, as for example in the case of difenzoquat, diquat or paraquat, suitable counterions forming an agriculturally acceptable salt illustratively include chloride, bromide, iodide, sulfate, phosphate, Zo acetate and succinate anions.
Where the herbicide is anionic or forms anions in the presence of a base, as for example in the case of most of the herbicides listed above with the exception of difenzoquat, diquat and paraquat, suitable counterions forming an agriculturally acceptable salt illustratively include sodium, potassium, ammonium, organic ammonium and organic sulfonium canons, wherein Zs organic ammonium or organic sulfonium cations have from 1 to about 16 carbon atoms.
Preferred organic ammonium canons are dimethylammonium, monoethanolammonium, n-propylammonium and isopropylammonium cations. Preferred organic sulfonium canons are trimethylsulfonium cations. Where the herbicide is glyphosate, especially preferred counterions are potassium and monoethanolammonium canons.
It will be understood that more than one water-soluble pesticide can be present and that, in such a case, the concentration ranges given above apply to the total content of water-soluble pesticides in the composition. Optionally a composition of the invention can contain, in addition to one or more water-soluble pesticides, one or more pesticides of lower water solubility. If present, a pesticide of low water solubility is typically located primarily in a discontinuous non-aqueous phase of the composition, for example an oil phase of an oil-in-water emulsion or a solid particulate phase of a suspension concentrate.
As indicated above, a composition of the invention contains an etheramine surfactant having, when in an aqueous medium at a pH of 4, the chemical formula (I) (Rs-~)X R4 R~-~~-R2) N+-R5 At_ m t v Rs_~ -R4 io where R1 is a C6_zz linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2_4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C~_4 alkyl or benzyl groups, R5 is hydrogen, a C1~
alkyl or benzyl is group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1~
alkylidene, t is 1 or 2, At- is a suitable anion, and v is 1 except where RS
is an anionic moiety in which case v is 0.
In preferred etheramines, Rl has at least about 8, more preferably about 12 to about 18 carbon atoms. All of the m (O-RZ) units are preferably alike and are preferably ethylene oxide, Zo isopropylene oxide or n-propylene oxide units. Where the (O-R2) units are ethylene oxide or propylene oxide units, m is preferably 1 to 5, most preferably 3 in the case of ethylene oxide units and most preferably 2 in the case of isopropylene oxide units. Where (O-RZ) is n-propylene oxide, m is preferably 1. All of the x+y (R3-O) units are preferably ethylene oxide, each of x and y is preferably at least l, and x+y is preferably 2 to about 15, more preferably 2 to about 7. R4 is groups are preferably hydrogen, except where x and y are 0, in which case R4 groups are preferably CI~ alkyl, more preferably methyl, groups.
_g_ Where R' is a C1_4 alkyl or benzyl group, the surfactant is a quaternary etheramine, more correctly a quaternary etherammonium salt. In quaternary etheramines R' is preferably a methyl group. The anion At- accompanying one or two etherammonium cations is preferably selected from chloride, bromide, iodide, sulfate, ethosulfate, phosphate, acetate, propionate, succinate, s lactate, citrate and tartrate anions and is most preferably chloride.
Illustrative examples of suitable quaternary etheramines are disclosed in above-cited U.S. Patent No.
5,750,468.
In a presently preferred embodiment of the invention, the surfactant is a tertiary etheramine corresponding to formula (I) wherein Rs is hydrogen. Note that formula (I) describes such a tertiary etheramine in its protonated form, as is typically present in an acidic aqueous to medium. When protonated, the tertiary etheramine is accompanied by an anion At-, which again can illustratively be chloride, bromide, iodide, sulfate, phosphate, acetate, succinate or tartrate, but which, in the presence of an acidic pesticide, can be an anion of that pesticide, for example a glyphosate anion. In a neutral to basic aqueous medium, the tertiary etheramine is typically non-protonated and is more accurately described by the chemical formula (II) R~-W-R2)m ERs-~~y R4 where R', R2, R3, R4, m, x and y are as defined for formula (I) above.
Illustrative examples of suitable tertiary etheramines are disclosed in above-cited U.S. Patent No.
5,750,468.
The concentration of etheramine surfactant in a composition of the invention is not narrowly critical, but is sufficient, in the absence of an anionic surfactant of formula (III), to Zo cause an increased level of skin and/or eye injuriousness by comparison with an otherwise similar composition in which the etheramine surfactant is replaced by water.
In particular, the concentration of etheramine is sufficient to increase the level of at least one injurious effect selected from eye irritation, skin irritation and skin sensitization, especially eye irritation and skin sensitization. Skin irritancy is believed to be a relatively rare property of etheramine Zs surfactants. Nonetheless, dermal and ocular safety is a very important consideration with any pesticide product. Thus the present invention has utility for those compositions wherein the etheramine concentration is sufficiently high to have adverse impact on any aspect of such safety, even if such impact is slight.
It is preferred that the concentration of etheramine surfactant is sufficient to provide substantially improved biological efficacy of the pesticide when the composition is diluted in a s suitable volume of water and applied to foliage of plants. Typically the weight ratio of etheramine surfactant to the water-soluble pesticide is about 1:10 to about 2:1. Illustratively, where the water-soluble pesticide is a salt of glyphosate, the weight ratio of etheramine surfactant to glyphosate a.e. is preferably about 1:9 to about 1:3.
Optionally, more than one etheramine surfactant can be present; in such a case amounts io or concentrations given herein in relation to an etheramine surfactant are to be considered to apply to the total amount or concentration of etheramine surfactants present.
At the heart of the invention is the presence of an anionic surfactant having the chemical formula (III) R'-(O-R$)~ X
is where R' is a C4_22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8_12 alkyl)phenyl group, Rg groups are independently CZ~ alkylidene groups, n is 0 to about 60 and X
is an anionic radical, selected from carboxylate (-COO-), ether carboxylate (-OCHZCOO-), sulfate (-OS03-) and phosphate (-OP03H- and -OP032-). Surprisingly the anionic surfactant reduces the level of injuriousness of the composition to skin and/or eyes that is imparted by the Zo etheramine surfactant. In particular, where the etheramine surfactant imparts or contributes to injuriousness in the form of eye irritation or skin sensitization, the injuriousness is moderated or eliminated by the presence of the anionic surfactant. According to one embodiment of the invention, replacement of a minor portion (not more than about one half) of the etheramine surfactant by an equal weight of the anionic surfactant improves dermal and/or ocular safety of Zs the composition. According to another embodiment of the invention, addition of the anionic surfactant without reduction in the amount of etheramine surfactant present improves dermal and/or ocular safety of the composition.
The weight ratio of the anionic surfactant to the etheramine surfactant is not less than about 1:10 and not greater than about 1:1. Surprisingly, benefits in improved dermal and/or so ocular safety are obtainable at low weight ratios of anionic surfactant to etheramine surfactant, for example about 1:10 to about 1:4. Preferred weight ratios of anionic surfactant to etheramine surfactant are about 1:8 to about 1:5.
Optionally, more than one anionic surfactant can be present; in such a case amounts or concentrations given herein in relation to an anionic surfactant are to be considered to apply to s the total amount or concentration of anionic surfactants present.
Illustrative classes of anionic surfactant having utility in compositions of the invention include alkyl carboxylates such as fatty acids, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkylphenyl ether carboxylates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates (including those with ring sulfonation), io mono- and dialkyl phosphates, mono- and di(polyoxyethylene alkyl ether) phosphates, mono-and di(polyoxyethylene alkylphenyl ether) phosphates, and salts thereof.
Suitable cationic counterions in the case of such salts illustratively include sodium, potassium, ammonium, dimethylammonium, isopropylammonium, monoethanolammonium and trimethylsulfonium cations. The etheramine surfactant, in the form of etherammonium canons, can also form a salt i s with the anionic surfactant.
In preferred anionic surfactants, R' in formula (III) is a (C8_12 alkyl)phenyl, e.g., octylphenyl, nonylphenyl or dodecylphenyl, or a Cg_ZZ, more preferably Ci2-ls, linear or branched, saturated or unsaturated, aliphatic hydrocarbyl group. Suitable aliphatic hydrocarbyl groups include without restriction lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl, linoleyl, zo linolenyl and isotridecyl groups. Conveniently such aliphatic hydrocarbyl groups can be derived from natural oils or fats and comprise mixtures of fatty alkyl chains such as cocoalkyl and tallowalkyl chains. (The term "alkyl" as used in surfactant nomenclature does not necessarily indicate full saturation.) (O-Rg) units in formula (III) are preferably ethylene oxide units. The number of such Zs units (n) is preferably 0 to about 10.
In a presently preferred embodiment of the invention, X in formula (III) is phosphate, and accordingly the anionic surfactant is a monoalkyl ether phosphate or a mono(alkylphenyl) ether phosphate. Such a phosphate monoester is generally accompanied by the corresponding diester;
amounts or concentrations of phosphate ester surfactants recited herein are to be understood to 3o apply to the total of mono- and diesters. Preferably the monoester:diester weight ratio is greater than about 1:1, more preferably greater than about 2:1. In principle the phosphate surfactant can all be present as the monoester, but in practice it is difficult, and unnecessary, to ensure the absence of diester.
Inert or excipient ingredients other than water, the etheramine surfactant and the anionic s surfactant can optionally be included in a composition of the invention.
Such ingredients include surfactants other than those of formula (I) or formula (III), for example polyoxyethylene alkylamines, alkylammonium salts and nonionic surfactants such as polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers, sorbitan esters and alkyl polyglycosides.
Other optional excipient ingredients include oils, solvents, stabilizing agents, antifreeze agents and pour point io depressants such as glycols, dyes, inorganic salts such as ammonium sulfate, fertilizers, foam moderating agents, thickeners, drift control agents, etc.
The present invention is not limited by the method used to assess any aspect of injuriousness to skin or eyes, including eye irritation and skin sensitization. However, eye irritation can be assessed by means of the Draize test or a suitable modification thereof and skin is sensitization by means of the Buehler test or a suitable modification thereof. Specific method protocols can be found in U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F, Guideline 81-4 (Draize test), and Guideline 81-6 (modified Buehler test).
EXAMPLES
Zo Compositions of Examples 1 and 2 hereinbelow all contain an etheramine surfactant of formula (II) Rt-U-R2)m ~R3-O)y R4 where Rl is Ci2-14 alkyl, (O-R2) units are isopropylene oxide units, m is 2, (O-R3) units are ethylene oxide units, x+y is an average number of 5, and R4 is hydrogen. This surfactant is is referred to in the Examples as Etheramine I.
Compositions of the invention illustrated in Examples 1 and 2 further contain an anionic surfactant that is a mixture of phosphate mono- and diesters of polyoxyethylene (4) isotridecyl W~ X1/0$22$ CA 02375949 2001-12-14 pCT/i1S00/19317 ether in a weight ratio of about 7 parts monoester to 3 parts diester. This surfactant is referred to in the Examples as Phosphate I.
Composition A, included in Examples 1 and 2 as a comparative reference, is a water-soluble concentrate formulation of glyphosate isopropylammonium salt. It is prepared from s MON 0139, a concentrated aqueous solution of glyphosate isopropylammonium salt having an assay of 46% glyphosate acid equivalent (a.e.). Ingredients (all percentages are by weight) of Composition A are:
MON 0139 (46.0% a.e.) 86.96%
Etheramine I 10.00%
io Deionized water 3.04%
The glyphosate a.e. concentration of Composition A is 40% by weight or 482 g/1.
Composition A has a specific gravity (20/15.6°C) of 1.2053 and has a cloud point higher than 90°C, indicating excellent high temperature stability.
Composition B is a composition of the present invention having the following ingredients is (all percentages are by weight):
MON 0139 (46.0% a.e.) 86.96%
Etheramine I 10.00%
Phosphate I 1.00%
Deionized water 2.04%
Zo The glyphosate a.e. concentration of Composition B is 40% by weight or 483 g/1.
Composition B has a specific gravity (20/15.6°C) of 1.2086 and has a cloud point of 77°C, indicating excellent high temperature stability.
Composition C is a composition of the present invention having the following ingredients (all percentages are by weight):
is MON 0139 (45.8% a.e.) 87.34%
Etheramine I 8.80%
Phosphate I 1.26%
Deionized water 2.60%
The glyphosate a.e. concentration of Composition C is 40% by weight or 483 g/1.
Composition C has a specific gravity (20/15.6°C) of 1.2076 and has a cloud point of 80°C, indicating excellent high temperature stability.
Composition D is a composition of the present invention having the following ingredients s (all percentages are by weight):
MON 0139 (45.8% a.e.) 81.00%
Etheramine I 8.16%
Phosphate I 1.17%
Deionized water 9.67%
io The glyphosate a.e. concentration of Composition D is 37% by weight or 442 g/1.
Composition D has a specific gravity (20/15.6°C) of 1.1945 and has a cloud point of 74°C, indicating excellent high temperature stability.
In reading the Examples that follow, it should be understood that the eye irritation and skin sensitization effects evident for Composition A are entirely attributable to the surfactant is component of that composition, MON 0139 itself being non-irritant to eyes and non-sensitizing to skin.
Example 1 Compositions A-D were tested for eye irritation by the Draize test following Guideline 81-4 of U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F.
zo Compositions were administered in a single 0.1 ml dose, undiluted, to the conjunctiva) sac of the right eye of 6 New Zealand White rabbits. Corneal opacity, iris lesions and conjunctiva) redness, chemosis and discharge were each assessed at eight times after dose administration, on a standardized scale of 0-3, where 0 indicates no effect and 3 the most severe effect. Average scores were as shown in Tables 1-3.
is Table 1. Average corneal opacity scores Time after dose: 1 1 2 d 3 7 10 14 21 h d d d d d d Composition A 1.5 1.8 1.7 1.7 1.0 0.8 0.5 0.5 Composition B 1.0 1.2 1.7 1.7 1.2 0.7 0.7 0.3 Composition C 0.8 1.3 1.7 1.2 0.0 0.0 0.0 0.0 Composition D 0.7 1.7 1.3 1.0 0.2 0.0 0.0 0.0 WO 01/0$225 CA 02375949 2001-12-14 PCT/US00/19317 Table 2. Average iris lesion scores Time after dose: 1 1 Z 3 7 10 14 21 h d d d d d d d Composition A 1.0 1.0 0.8 0.5 0.2 0.2 0.2 0.0 Composition B 1.0 1.0 0.8 0.7 0.3 0.0 0.0 0.0 Composition C 1.0 0.8 0.3 0.2 0.2 0.0 0.0 0.0 Composition D 1.0 1.0 1.0 0.7 0.0 0.0 0.0 0.0 Table 3. Average conjunctiva) injury scores (redness, chemosis and discharge) Time after dose: 1 1 2 3 7 10 14 21 h d d d d d d d Composition A 2.2 2.0 1.8 1.6 0.7 0.6 0.4 0.2 Composition B 1.8 1.9 1.9 1.7 1.1 0.6 0.5 0.3 Composition C 1.9 1.8 1.4 1.1 0.5 0.1 0.0 0.0 -Composition D ~1.5 ~ 1.4 1.1 0.4 0.0 0.0 0.0 1.8 s It should be noted that in the tests of this Example, treated eyes were not washed to remove the administered composition. Prolonged exposure effects shown above are not necessarily indicative of effects where, as is most likely, accidental contact of an irritant composition with the eye is followed within a short time by thorough washing to remove the irritant. Ocular injury as measured 1 hour after administration in the present tests is perhaps the io most relevant indicator of potential injuriousness of a composition with washing of the eye. It will be noted that corneal and conjunctiva) injury 1 hour after administration was lower for Compositions B, C and D of the invention than for the reference standard Composition A. At later times, Composition B gave similar injury scores to Composition A, but Compositions C and D of the invention were markedly less injurious, showing improved recovery over a 21-day is period from the early effects of administration to the eye.
Example 2 Compositions A and D were tested for dermal sensitization by the modified Buehler test following Guideline 81-6 of U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F. An induction dose of 0.4 ml of each composition was administered zo undiluted to the clipped, intact skin of 10 albino guinea pigs using a Hilltop Chamber and' occlusive dressing, once weekly for three weeks, for 6 hours each. A single challenge dose of 0.4 ml was administered undiluted to a naive skin site two weeks after the last induction dose, for WO 01/0$225 CA 02375949 2001-12-14 pCT/US00/19317 6 hours. A single rechallenge dose of 0.4 ml of a 50% dilution of the composition in deionized water was administered three weeks after the last induction dose, for 6 hours.
The results indicated that Composition A caused dermal sensitization, while Composition B did not cause dermal sensitization, in guinea pigs.
s The preceding description of specific embodiments of the present invention is not intended to be a complete list of every possible embodiment of the invention.
Persons skilled in this field will recognize that modifications can be made to the specific embodiments described here that remain within the scope of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to aqueous concentrate compositions, including io formulations known in the art as soluble concentrates (SL), oil-in-water emulsions (EW), water-based suspension concentrates (SC) and suspoemulsions (SE). In all cases a water-soluble pesticide is present in solution in an aqueous phase of the composition. The concentration of the water-soluble pesticide is expressed herein on an active ingredient (a.i.) basis except where the active ingredient is a salt of a biologically active acid, in which case the concentration is is expressed on an acid equivalent (a.e.) basis. The concentration of pesticide (a.i. or a.e. as appropriate) in the composition as a whole ranges from about 50 to about 600 g/1; preferred compositions have a pesticide concentration of about 360 to about 540 g/1.
A "water-soluble" pesticide herein, including a salt or other water-soluble derivative of a pesticide, is one having a solubility in deionized water at 20°C of not less than about 50 g/1, more ao preferably not less than about 200 g/1.
Water-soluble fungicides and bactericides useful in compositions of the invention illustratively include borax, sec-butylamine, calcium polysulfide, copper sulfate, fosetyl, guazatine, hydroxyquinoline sulfate, iminoctadine, kasugamycin, mercuric chloride, metam, nabam, polyoxin B, propamocarb and validamycin and/or water-soluble salts thereof. Water-Zs soluble insecticides, acaricides and nematicides useful in compositions of the invention illustratively include acephate, butoxycarboxim, cartap, dicrotophos, formetanate, hydrogen cyanide, methamidophos, methomyl, mevinphos, monocrotophos, nicotine, nitenpyram, omethoate, oxamyl, oxydemeton-methyl, phosphamidon, thiocyclam, trichlorfon and vamidothion and/or water-soluble salts thereof. Water-soluble plant growth regulators useful in 3o compositions of the invention illustratively include chlormequat, chlorphonium, clofencet, cloxyfonac, cyanamide, daminozide, dikegulac, ethephon and mepiquat and/or water-soluble salts thereof.
In one embodiment of the invention, the water-soluble pesticide is a herbicide or an agriculturally acceptable salt thereof, including without restriction salts of acifluorfen, asulam, s benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, fluazifop, fluoroglycofen, fomesafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, io sulfamic acid, 2,3,6-TBA, TCA and triclopyr.
Preferred water-soluble herbicides are salts of acid compounds whose molecular structure comprises at least one of each of amine, carboxylate, and either phosphonate or phosphinate functional groups. This category includes salts of the herbicides N-phosphonomethylglycine (glyphosate) and DL-homoalanin-4-yl(methyl)phosphinate (glufosinate). Another preferred is group of herbicides are salts of compounds of the imidazolinone class, including imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin and imazethapyr.
Where the herbicide is cationic or forms canons in the presence of an acid, as for example in the case of difenzoquat, diquat or paraquat, suitable counterions forming an agriculturally acceptable salt illustratively include chloride, bromide, iodide, sulfate, phosphate, Zo acetate and succinate anions.
Where the herbicide is anionic or forms anions in the presence of a base, as for example in the case of most of the herbicides listed above with the exception of difenzoquat, diquat and paraquat, suitable counterions forming an agriculturally acceptable salt illustratively include sodium, potassium, ammonium, organic ammonium and organic sulfonium canons, wherein Zs organic ammonium or organic sulfonium cations have from 1 to about 16 carbon atoms.
Preferred organic ammonium canons are dimethylammonium, monoethanolammonium, n-propylammonium and isopropylammonium cations. Preferred organic sulfonium canons are trimethylsulfonium cations. Where the herbicide is glyphosate, especially preferred counterions are potassium and monoethanolammonium canons.
It will be understood that more than one water-soluble pesticide can be present and that, in such a case, the concentration ranges given above apply to the total content of water-soluble pesticides in the composition. Optionally a composition of the invention can contain, in addition to one or more water-soluble pesticides, one or more pesticides of lower water solubility. If present, a pesticide of low water solubility is typically located primarily in a discontinuous non-aqueous phase of the composition, for example an oil phase of an oil-in-water emulsion or a solid particulate phase of a suspension concentrate.
As indicated above, a composition of the invention contains an etheramine surfactant having, when in an aqueous medium at a pH of 4, the chemical formula (I) (Rs-~)X R4 R~-~~-R2) N+-R5 At_ m t v Rs_~ -R4 io where R1 is a C6_zz linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2_4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C~_4 alkyl or benzyl groups, R5 is hydrogen, a C1~
alkyl or benzyl is group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1~
alkylidene, t is 1 or 2, At- is a suitable anion, and v is 1 except where RS
is an anionic moiety in which case v is 0.
In preferred etheramines, Rl has at least about 8, more preferably about 12 to about 18 carbon atoms. All of the m (O-RZ) units are preferably alike and are preferably ethylene oxide, Zo isopropylene oxide or n-propylene oxide units. Where the (O-R2) units are ethylene oxide or propylene oxide units, m is preferably 1 to 5, most preferably 3 in the case of ethylene oxide units and most preferably 2 in the case of isopropylene oxide units. Where (O-RZ) is n-propylene oxide, m is preferably 1. All of the x+y (R3-O) units are preferably ethylene oxide, each of x and y is preferably at least l, and x+y is preferably 2 to about 15, more preferably 2 to about 7. R4 is groups are preferably hydrogen, except where x and y are 0, in which case R4 groups are preferably CI~ alkyl, more preferably methyl, groups.
_g_ Where R' is a C1_4 alkyl or benzyl group, the surfactant is a quaternary etheramine, more correctly a quaternary etherammonium salt. In quaternary etheramines R' is preferably a methyl group. The anion At- accompanying one or two etherammonium cations is preferably selected from chloride, bromide, iodide, sulfate, ethosulfate, phosphate, acetate, propionate, succinate, s lactate, citrate and tartrate anions and is most preferably chloride.
Illustrative examples of suitable quaternary etheramines are disclosed in above-cited U.S. Patent No.
5,750,468.
In a presently preferred embodiment of the invention, the surfactant is a tertiary etheramine corresponding to formula (I) wherein Rs is hydrogen. Note that formula (I) describes such a tertiary etheramine in its protonated form, as is typically present in an acidic aqueous to medium. When protonated, the tertiary etheramine is accompanied by an anion At-, which again can illustratively be chloride, bromide, iodide, sulfate, phosphate, acetate, succinate or tartrate, but which, in the presence of an acidic pesticide, can be an anion of that pesticide, for example a glyphosate anion. In a neutral to basic aqueous medium, the tertiary etheramine is typically non-protonated and is more accurately described by the chemical formula (II) R~-W-R2)m ERs-~~y R4 where R', R2, R3, R4, m, x and y are as defined for formula (I) above.
Illustrative examples of suitable tertiary etheramines are disclosed in above-cited U.S. Patent No.
5,750,468.
The concentration of etheramine surfactant in a composition of the invention is not narrowly critical, but is sufficient, in the absence of an anionic surfactant of formula (III), to Zo cause an increased level of skin and/or eye injuriousness by comparison with an otherwise similar composition in which the etheramine surfactant is replaced by water.
In particular, the concentration of etheramine is sufficient to increase the level of at least one injurious effect selected from eye irritation, skin irritation and skin sensitization, especially eye irritation and skin sensitization. Skin irritancy is believed to be a relatively rare property of etheramine Zs surfactants. Nonetheless, dermal and ocular safety is a very important consideration with any pesticide product. Thus the present invention has utility for those compositions wherein the etheramine concentration is sufficiently high to have adverse impact on any aspect of such safety, even if such impact is slight.
It is preferred that the concentration of etheramine surfactant is sufficient to provide substantially improved biological efficacy of the pesticide when the composition is diluted in a s suitable volume of water and applied to foliage of plants. Typically the weight ratio of etheramine surfactant to the water-soluble pesticide is about 1:10 to about 2:1. Illustratively, where the water-soluble pesticide is a salt of glyphosate, the weight ratio of etheramine surfactant to glyphosate a.e. is preferably about 1:9 to about 1:3.
Optionally, more than one etheramine surfactant can be present; in such a case amounts io or concentrations given herein in relation to an etheramine surfactant are to be considered to apply to the total amount or concentration of etheramine surfactants present.
At the heart of the invention is the presence of an anionic surfactant having the chemical formula (III) R'-(O-R$)~ X
is where R' is a C4_22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8_12 alkyl)phenyl group, Rg groups are independently CZ~ alkylidene groups, n is 0 to about 60 and X
is an anionic radical, selected from carboxylate (-COO-), ether carboxylate (-OCHZCOO-), sulfate (-OS03-) and phosphate (-OP03H- and -OP032-). Surprisingly the anionic surfactant reduces the level of injuriousness of the composition to skin and/or eyes that is imparted by the Zo etheramine surfactant. In particular, where the etheramine surfactant imparts or contributes to injuriousness in the form of eye irritation or skin sensitization, the injuriousness is moderated or eliminated by the presence of the anionic surfactant. According to one embodiment of the invention, replacement of a minor portion (not more than about one half) of the etheramine surfactant by an equal weight of the anionic surfactant improves dermal and/or ocular safety of Zs the composition. According to another embodiment of the invention, addition of the anionic surfactant without reduction in the amount of etheramine surfactant present improves dermal and/or ocular safety of the composition.
The weight ratio of the anionic surfactant to the etheramine surfactant is not less than about 1:10 and not greater than about 1:1. Surprisingly, benefits in improved dermal and/or so ocular safety are obtainable at low weight ratios of anionic surfactant to etheramine surfactant, for example about 1:10 to about 1:4. Preferred weight ratios of anionic surfactant to etheramine surfactant are about 1:8 to about 1:5.
Optionally, more than one anionic surfactant can be present; in such a case amounts or concentrations given herein in relation to an anionic surfactant are to be considered to apply to s the total amount or concentration of anionic surfactants present.
Illustrative classes of anionic surfactant having utility in compositions of the invention include alkyl carboxylates such as fatty acids, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkylphenyl ether carboxylates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates (including those with ring sulfonation), io mono- and dialkyl phosphates, mono- and di(polyoxyethylene alkyl ether) phosphates, mono-and di(polyoxyethylene alkylphenyl ether) phosphates, and salts thereof.
Suitable cationic counterions in the case of such salts illustratively include sodium, potassium, ammonium, dimethylammonium, isopropylammonium, monoethanolammonium and trimethylsulfonium cations. The etheramine surfactant, in the form of etherammonium canons, can also form a salt i s with the anionic surfactant.
In preferred anionic surfactants, R' in formula (III) is a (C8_12 alkyl)phenyl, e.g., octylphenyl, nonylphenyl or dodecylphenyl, or a Cg_ZZ, more preferably Ci2-ls, linear or branched, saturated or unsaturated, aliphatic hydrocarbyl group. Suitable aliphatic hydrocarbyl groups include without restriction lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl, linoleyl, zo linolenyl and isotridecyl groups. Conveniently such aliphatic hydrocarbyl groups can be derived from natural oils or fats and comprise mixtures of fatty alkyl chains such as cocoalkyl and tallowalkyl chains. (The term "alkyl" as used in surfactant nomenclature does not necessarily indicate full saturation.) (O-Rg) units in formula (III) are preferably ethylene oxide units. The number of such Zs units (n) is preferably 0 to about 10.
In a presently preferred embodiment of the invention, X in formula (III) is phosphate, and accordingly the anionic surfactant is a monoalkyl ether phosphate or a mono(alkylphenyl) ether phosphate. Such a phosphate monoester is generally accompanied by the corresponding diester;
amounts or concentrations of phosphate ester surfactants recited herein are to be understood to 3o apply to the total of mono- and diesters. Preferably the monoester:diester weight ratio is greater than about 1:1, more preferably greater than about 2:1. In principle the phosphate surfactant can all be present as the monoester, but in practice it is difficult, and unnecessary, to ensure the absence of diester.
Inert or excipient ingredients other than water, the etheramine surfactant and the anionic s surfactant can optionally be included in a composition of the invention.
Such ingredients include surfactants other than those of formula (I) or formula (III), for example polyoxyethylene alkylamines, alkylammonium salts and nonionic surfactants such as polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers, sorbitan esters and alkyl polyglycosides.
Other optional excipient ingredients include oils, solvents, stabilizing agents, antifreeze agents and pour point io depressants such as glycols, dyes, inorganic salts such as ammonium sulfate, fertilizers, foam moderating agents, thickeners, drift control agents, etc.
The present invention is not limited by the method used to assess any aspect of injuriousness to skin or eyes, including eye irritation and skin sensitization. However, eye irritation can be assessed by means of the Draize test or a suitable modification thereof and skin is sensitization by means of the Buehler test or a suitable modification thereof. Specific method protocols can be found in U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F, Guideline 81-4 (Draize test), and Guideline 81-6 (modified Buehler test).
EXAMPLES
Zo Compositions of Examples 1 and 2 hereinbelow all contain an etheramine surfactant of formula (II) Rt-U-R2)m ~R3-O)y R4 where Rl is Ci2-14 alkyl, (O-R2) units are isopropylene oxide units, m is 2, (O-R3) units are ethylene oxide units, x+y is an average number of 5, and R4 is hydrogen. This surfactant is is referred to in the Examples as Etheramine I.
Compositions of the invention illustrated in Examples 1 and 2 further contain an anionic surfactant that is a mixture of phosphate mono- and diesters of polyoxyethylene (4) isotridecyl W~ X1/0$22$ CA 02375949 2001-12-14 pCT/i1S00/19317 ether in a weight ratio of about 7 parts monoester to 3 parts diester. This surfactant is referred to in the Examples as Phosphate I.
Composition A, included in Examples 1 and 2 as a comparative reference, is a water-soluble concentrate formulation of glyphosate isopropylammonium salt. It is prepared from s MON 0139, a concentrated aqueous solution of glyphosate isopropylammonium salt having an assay of 46% glyphosate acid equivalent (a.e.). Ingredients (all percentages are by weight) of Composition A are:
MON 0139 (46.0% a.e.) 86.96%
Etheramine I 10.00%
io Deionized water 3.04%
The glyphosate a.e. concentration of Composition A is 40% by weight or 482 g/1.
Composition A has a specific gravity (20/15.6°C) of 1.2053 and has a cloud point higher than 90°C, indicating excellent high temperature stability.
Composition B is a composition of the present invention having the following ingredients is (all percentages are by weight):
MON 0139 (46.0% a.e.) 86.96%
Etheramine I 10.00%
Phosphate I 1.00%
Deionized water 2.04%
Zo The glyphosate a.e. concentration of Composition B is 40% by weight or 483 g/1.
Composition B has a specific gravity (20/15.6°C) of 1.2086 and has a cloud point of 77°C, indicating excellent high temperature stability.
Composition C is a composition of the present invention having the following ingredients (all percentages are by weight):
is MON 0139 (45.8% a.e.) 87.34%
Etheramine I 8.80%
Phosphate I 1.26%
Deionized water 2.60%
The glyphosate a.e. concentration of Composition C is 40% by weight or 483 g/1.
Composition C has a specific gravity (20/15.6°C) of 1.2076 and has a cloud point of 80°C, indicating excellent high temperature stability.
Composition D is a composition of the present invention having the following ingredients s (all percentages are by weight):
MON 0139 (45.8% a.e.) 81.00%
Etheramine I 8.16%
Phosphate I 1.17%
Deionized water 9.67%
io The glyphosate a.e. concentration of Composition D is 37% by weight or 442 g/1.
Composition D has a specific gravity (20/15.6°C) of 1.1945 and has a cloud point of 74°C, indicating excellent high temperature stability.
In reading the Examples that follow, it should be understood that the eye irritation and skin sensitization effects evident for Composition A are entirely attributable to the surfactant is component of that composition, MON 0139 itself being non-irritant to eyes and non-sensitizing to skin.
Example 1 Compositions A-D were tested for eye irritation by the Draize test following Guideline 81-4 of U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F.
zo Compositions were administered in a single 0.1 ml dose, undiluted, to the conjunctiva) sac of the right eye of 6 New Zealand White rabbits. Corneal opacity, iris lesions and conjunctiva) redness, chemosis and discharge were each assessed at eight times after dose administration, on a standardized scale of 0-3, where 0 indicates no effect and 3 the most severe effect. Average scores were as shown in Tables 1-3.
is Table 1. Average corneal opacity scores Time after dose: 1 1 2 d 3 7 10 14 21 h d d d d d d Composition A 1.5 1.8 1.7 1.7 1.0 0.8 0.5 0.5 Composition B 1.0 1.2 1.7 1.7 1.2 0.7 0.7 0.3 Composition C 0.8 1.3 1.7 1.2 0.0 0.0 0.0 0.0 Composition D 0.7 1.7 1.3 1.0 0.2 0.0 0.0 0.0 WO 01/0$225 CA 02375949 2001-12-14 PCT/US00/19317 Table 2. Average iris lesion scores Time after dose: 1 1 Z 3 7 10 14 21 h d d d d d d d Composition A 1.0 1.0 0.8 0.5 0.2 0.2 0.2 0.0 Composition B 1.0 1.0 0.8 0.7 0.3 0.0 0.0 0.0 Composition C 1.0 0.8 0.3 0.2 0.2 0.0 0.0 0.0 Composition D 1.0 1.0 1.0 0.7 0.0 0.0 0.0 0.0 Table 3. Average conjunctiva) injury scores (redness, chemosis and discharge) Time after dose: 1 1 2 3 7 10 14 21 h d d d d d d d Composition A 2.2 2.0 1.8 1.6 0.7 0.6 0.4 0.2 Composition B 1.8 1.9 1.9 1.7 1.1 0.6 0.5 0.3 Composition C 1.9 1.8 1.4 1.1 0.5 0.1 0.0 0.0 -Composition D ~1.5 ~ 1.4 1.1 0.4 0.0 0.0 0.0 1.8 s It should be noted that in the tests of this Example, treated eyes were not washed to remove the administered composition. Prolonged exposure effects shown above are not necessarily indicative of effects where, as is most likely, accidental contact of an irritant composition with the eye is followed within a short time by thorough washing to remove the irritant. Ocular injury as measured 1 hour after administration in the present tests is perhaps the io most relevant indicator of potential injuriousness of a composition with washing of the eye. It will be noted that corneal and conjunctiva) injury 1 hour after administration was lower for Compositions B, C and D of the invention than for the reference standard Composition A. At later times, Composition B gave similar injury scores to Composition A, but Compositions C and D of the invention were markedly less injurious, showing improved recovery over a 21-day is period from the early effects of administration to the eye.
Example 2 Compositions A and D were tested for dermal sensitization by the modified Buehler test following Guideline 81-6 of U.S. Environmental Protection Agency Pesticide Assessment Guidelines, Subdivision F. An induction dose of 0.4 ml of each composition was administered zo undiluted to the clipped, intact skin of 10 albino guinea pigs using a Hilltop Chamber and' occlusive dressing, once weekly for three weeks, for 6 hours each. A single challenge dose of 0.4 ml was administered undiluted to a naive skin site two weeks after the last induction dose, for WO 01/0$225 CA 02375949 2001-12-14 pCT/US00/19317 6 hours. A single rechallenge dose of 0.4 ml of a 50% dilution of the composition in deionized water was administered three weeks after the last induction dose, for 6 hours.
The results indicated that Composition A caused dermal sensitization, while Composition B did not cause dermal sensitization, in guinea pigs.
s The preceding description of specific embodiments of the present invention is not intended to be a complete list of every possible embodiment of the invention.
Persons skilled in this field will recognize that modifications can be made to the specific embodiments described here that remain within the scope of the present invention.
Claims (11)
1. An aqueous concentrate pesticidal composition comprising (a) about 50 to about 500 g/l of a water-soluble pesticide;
(b) an etheramine surfactant having, when present in an aqueous medium at a pH
of about 4, the chemical formula where R1 is a C6-22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2-4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C1-4 alkyl or benzyl groups, R5 is hydrogen, a C1-4 alkyl or benzyl group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1-4 alkylidene, t is 1 or 2, A t- is a suitable anion, and v is 1 except where R5 is an anionic moiety in which case v is 0;
said etheramine surfactant being in an amount sufficient, if it were the sole surfactant present, to increase the level of injuriousness of the composition to skin and/or eyes;
and (c) an anionic surfactant having the chemical formula R7-(O-R8)n-O-X
where R7 is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R8 groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate;
the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1.
(b) an etheramine surfactant having, when present in an aqueous medium at a pH
of about 4, the chemical formula where R1 is a C6-22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2-4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C1-4 alkyl or benzyl groups, R5 is hydrogen, a C1-4 alkyl or benzyl group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1-4 alkylidene, t is 1 or 2, A t- is a suitable anion, and v is 1 except where R5 is an anionic moiety in which case v is 0;
said etheramine surfactant being in an amount sufficient, if it were the sole surfactant present, to increase the level of injuriousness of the composition to skin and/or eyes;
and (c) an anionic surfactant having the chemical formula R7-(O-R8)n-O-X
where R7 is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R8 groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate;
the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1.
2. The composition of Claim 1 wherein the etheramine surfactant is a tertiary etheramine having, when non-protonated, the chemical formula where R1 is a C6-22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2-4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, and R4 groups are independently hydrogen, C1-4 alkyl or benzyl groups.
3. The composition of Claim 2 wherein, in the formula for the tertiary etheramine, R1 has about 12 to about 18 carbon atoms, (O-R2) units are ethylene oxide or isopropylene oxide units, m is 1 to 5, (R3-O) units are ethylene oxide units, each of x and y is at least 1, x+y is 2 to about 15, and R4 groups are hydrogen.
4. The composition of Claim 1 wherein the weight ratio of the etheramine surfactant to the water-soluble pesticide is about 1:10 to about 2:1.
5. The composition of Claim 1 wherein the anionic surfactant is selected from alkyl carboxylates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkylphenyl ether carboxylates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, mono- and dialkyl phosphates, mono- and di(polyoxyethylene alkyl ether) phosphates, mono- and di(polyoxyethylene alkylphenyl ether) phosphates, and salts thereof.
6. The composition of Claim 5 wherein the anionic surfactant is a mono(polyoxyethylene alkyl or alkylphenyl ether) phosphate or mixture thereof with the corresponding di(polyoxyethylene alkyl or alkylphenyl ether) phosphate, or a salt of such phosphate or of such mixture of phosphates.
7. The composition of Claim 1 wherein the water-soluble pesticide is selected from borax, sec-butylamine, calcium polysulfide, copper sulfate, fosetyl, guazatine, hydroxyquinoline sulfate, iminoctadine, kasugamycin, mercuric chloride, metam, nabam, polyoxin B, propamocarb, validamycin, acephate, butoxycarboxim, cartap, dicrotophos, formetanate, hydrogen cyanide, methamidophos, methomyl, mevinphos, monocrotophos, nicotine, nitenpyram, omethoate, oxamyl, oxydemeton-methyl, phosphamidon, thiocyclam, trichlorfon, vamidothion, chlormequat, chlorphonium, clofencet, cloxyfonac, cyanamide, daminozide, dikegulac, ethephon, mepiquat, acifluorfen, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, fluazifop, fluoroglycofen, fomesafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and salts thereof.
8. The composition of Claim 1 wherein the water-soluble pesticide is a salt of the herbicide glyphosate.
9. The composition of Claim 8 wherein the water-soluble pesticide is the potassium salt of glyphosate.
10. The composition of Claim 8 wherein the water-soluble pesticide is the monoethanolammonium salt of glyphosate.
11. In an aqueous concentrate pesticidal composition comprising a water-soluble pesticide and an etheramine surfactant having, when present in an aqueous medium at a pH of about 4, the chemical formula where R1 is a C6-22 linear or branched, saturated or unsaturated aliphatic hydrocarbyl group, R2 and R3 groups are independently C2-4 alkylidene groups, m is an average number of 1 to about 5, x and y are average numbers such that x+y is an average number of 0 to about 60, R4 groups are independently hydrogen, C1-4 alkyl or benzyl groups, R5 is hydrogen, a C1-4 alkyl or benzyl group or an anionic moiety selected from oxide (-O-) and -R6-COO- groups wherein R6 is C1-4 alkylidene, t is 1 or 2, A t- is a suitable anion, and v is 1 except where R5 is an anionic moiety in which case v is 0; the improvement comprising addition, at a weight ratio to the etheramine surfactant of about 1:10 to about 1:1, of an anionic surfactant having the chemical formula R7-(O-R8)n-O-X
where R7 is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R8 groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate.
where R7 is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R8 groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US14452899P | 1999-07-19 | 1999-07-19 | |
US60/144,528 | 1999-07-19 | ||
PCT/US2000/019317 WO2001005225A1 (en) | 1999-07-19 | 2000-07-17 | Aqueous concentrate pesticidal compositions having improved dermal and ocular safety |
Publications (1)
Publication Number | Publication Date |
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CA2375949A1 true CA2375949A1 (en) | 2001-01-25 |
Family
ID=22508995
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002375949A Abandoned CA2375949A1 (en) | 1999-07-19 | 2000-07-17 | Aqueous concentrate pesticidal compositions having improved dermal and ocular safety |
Country Status (13)
Country | Link |
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EP (1) | EP1199928A1 (en) |
JP (1) | JP5529361B2 (en) |
CN (1) | CN1361662A (en) |
AR (1) | AR024801A1 (en) |
AU (1) | AU6215900A (en) |
BR (1) | BR0012549A (en) |
CA (1) | CA2375949A1 (en) |
CZ (1) | CZ2002174A3 (en) |
EA (1) | EA200200180A1 (en) |
HU (1) | HUP0202309A3 (en) |
MX (1) | MXPA02000622A (en) |
WO (1) | WO2001005225A1 (en) |
ZA (1) | ZA200110533B (en) |
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JP2004527565A (en) * | 2001-05-08 | 2004-09-09 | モンサント・ヨーロツプ・ソシエテ・アノニム | Glyphosate composition and use thereof |
DE10325199A1 (en) * | 2003-06-04 | 2004-12-23 | Clariant Gmbh | Preparations containing amine oxides and anionic surfactants |
US9192158B2 (en) | 2008-12-11 | 2015-11-24 | Monsanto Technology Llc | Herbicide formulations containing an etheramine and alkylamine alkoxylate surfactant system |
CN103766396B (en) * | 2014-01-16 | 2015-09-23 | 江苏集贤绿色化学科技研究院有限公司 | A kind of insecticide for lepidoptera pest and preparation method thereof |
ZA201508496B (en) * | 2014-12-03 | 2018-05-30 | Bitrad Trust | Stabililized liquid acephate pesticide formulation |
CN105454239A (en) * | 2015-12-20 | 2016-04-06 | 广东中迅农科股份有限公司 | Anti-hydrolytic nitenpyram aqueous solution and preparation method thereof |
CN110839632A (en) * | 2018-08-20 | 2020-02-28 | 四川利尔作物科学有限公司 | Weeding composition |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US5703015A (en) * | 1990-08-09 | 1997-12-30 | Monsanto Company | Pesticidal compositions of polyoxyalkylene alkylamine surfactants having reduced eye irritation |
CA2047968C (en) * | 1990-08-09 | 2000-05-23 | Paul D. Berger | New surfactant compositions, method for their preparation, and pesticidal compositions containing same |
US5389598A (en) * | 1993-12-17 | 1995-02-14 | Monsanto Company | Aqueous concentrate formulations having reduced eye irritancy |
JP3015107B2 (en) * | 1995-04-10 | 2000-03-06 | モンサント・カンパニー | Glyphosate formulations containing etheramine surfactants |
-
2000
- 2000-07-17 HU HU0202309A patent/HUP0202309A3/en unknown
- 2000-07-17 EA EA200200180A patent/EA200200180A1/en unknown
- 2000-07-17 BR BR0012549-0A patent/BR0012549A/en not_active Application Discontinuation
- 2000-07-17 MX MXPA02000622A patent/MXPA02000622A/en unknown
- 2000-07-17 EP EP00948692A patent/EP1199928A1/en not_active Withdrawn
- 2000-07-17 CA CA002375949A patent/CA2375949A1/en not_active Abandoned
- 2000-07-17 CN CN00810524.3A patent/CN1361662A/en active Pending
- 2000-07-17 AU AU62159/00A patent/AU6215900A/en not_active Abandoned
- 2000-07-17 WO PCT/US2000/019317 patent/WO2001005225A1/en not_active Application Discontinuation
- 2000-07-17 CZ CZ2002174A patent/CZ2002174A3/en unknown
- 2000-07-17 JP JP2001510303A patent/JP5529361B2/en not_active Expired - Lifetime
- 2000-07-20 AR ARP000103724A patent/AR024801A1/en unknown
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2001
- 2001-12-21 ZA ZA200110533A patent/ZA200110533B/en unknown
Also Published As
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BR0012549A (en) | 2002-04-09 |
HUP0202309A2 (en) | 2002-10-28 |
ZA200110533B (en) | 2003-03-24 |
JP5529361B2 (en) | 2014-06-25 |
WO2001005225A1 (en) | 2001-01-25 |
CN1361662A (en) | 2002-07-31 |
EA200200180A1 (en) | 2002-06-27 |
JP2003504381A (en) | 2003-02-04 |
HUP0202309A3 (en) | 2002-12-28 |
CZ2002174A3 (en) | 2002-07-17 |
MXPA02000622A (en) | 2002-07-02 |
AU6215900A (en) | 2001-02-05 |
EP1199928A1 (en) | 2002-05-02 |
AR024801A1 (en) | 2002-10-23 |
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