IL98717A - Herbicidal agents based on a combination of metamitron/ethofumesate/phenmedipham/desmedipham - Google Patents
Herbicidal agents based on a combination of metamitron/ethofumesate/phenmedipham/desmediphamInfo
- Publication number
- IL98717A IL98717A IL9871791A IL9871791A IL98717A IL 98717 A IL98717 A IL 98717A IL 9871791 A IL9871791 A IL 9871791A IL 9871791 A IL9871791 A IL 9871791A IL 98717 A IL98717 A IL 98717A
- Authority
- IL
- Israel
- Prior art keywords
- weight
- parts
- iii
- active compounds
- metamitron
- Prior art date
Links
- IDOWTHOLJBTAFI-UHFFFAOYSA-N phenmedipham Chemical compound COC(=O)NC1=CC=CC(OC(=O)NC=2C=C(C)C=CC=2)=C1 IDOWTHOLJBTAFI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- IRCMYGHHKLLGHV-UHFFFAOYSA-N 2-ethoxy-3,3-dimethyl-2,3-dihydro-1-benzofuran-5-yl methanesulfonate Chemical compound C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 IRCMYGHHKLLGHV-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000005512 Ethofumesate Substances 0.000 title claims abstract description 53
- 239000005594 Phenmedipham Substances 0.000 title claims abstract description 53
- VHCNQEUWZYOAEV-UHFFFAOYSA-N metamitron Chemical compound O=C1N(N)C(C)=NN=C1C1=CC=CC=C1 VHCNQEUWZYOAEV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000005579 Metamitron Substances 0.000 title claims abstract description 49
- WZJZMXBKUWKXTQ-UHFFFAOYSA-N desmedipham Chemical compound CCOC(=O)NC1=CC=CC(OC(=O)NC=2C=CC=CC=2)=C1 WZJZMXBKUWKXTQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005503 Desmedipham Substances 0.000 title claims abstract description 22
- 239000004009 herbicide Substances 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 117
- 238000009472 formulation Methods 0.000 claims abstract description 77
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- 150000001875 compounds Chemical class 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims description 15
- 239000005995 Aluminium silicate Substances 0.000 claims description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000080 wetting agent Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 238000007873 sieving Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 8
- 230000002363 herbicidal effect Effects 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 239000002689 soil Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
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- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 125000005624 silicic acid group Chemical class 0.000 description 3
- 240000005702 Galium aparine Species 0.000 description 2
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- 241000209510 Liliopsida Species 0.000 description 2
- 241000221026 Mercurialis annua Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 241001233957 eudicotyledons Species 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- 239000011707 mineral Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 1
- 241000219144 Abutilon Species 0.000 description 1
- 241000209136 Agropyron Species 0.000 description 1
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- 241000219318 Amaranthus Species 0.000 description 1
- 244000237956 Amaranthus retroflexus Species 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- 240000006694 Stellaria media Species 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 210000003050 axon Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 229960000278 theophylline Drugs 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to novel ready-for-use formulations of the known herbicidal active substances metamitron (I) + ethofumesate (II) + (A) phenmedipham (III) or (B) phenmedipham (III) and desmedipham (IV) or (C) desmidipham (IV), preferably solid formulations such as water-dispersible powders (WP) or water-dispersible granules (WG), the ratio by weight of the active substances (I):(II):(III) or (IV) being (1):(0.05 to 1):(0.05 to 1), that of the active substances (I):(II):(III):(IV) being (1):(0.05 to 1):(0.05 to 1):(0.05 to 1), and the total active substance content in each case being between 20 and 75% by weight, and to their use as herbicides, in particular as selective herbicides in beet.
Description
ON*. >*τοχΤ/ΟΝΟ >*τja/οοη131m/) 1no>axon Herbicidal agents based on a combination of metamitron/ethofumesate/phenmedipham/desmedipham BAYER AKTIENGESELLSCHAFT C: 83621 The invention relates to new finished formulations of the known herbicidal active substances metamitron + ethofume- sate + (A) phenmedipham, or (B) phenmedipham + desmedipham or (C) desmedipham, preferably solid formulations such as water-dispersible powders (WP) and water-dispersible granules (WG) , and their use as herbicides, in particular as selective beet herbicides .
Mixtures of these active compounds have previously been described, ditto tank mixes of a finished formulation of ethofumesate + phenmedipham with metamitron (cf. J. Marshall et al, 1987, British Crop Protection Conference Weeds (1), page 233-240), which have proved suitable in practice for selective combating of weeds in beet cultures.. However, the disadvantage of these tank mixes is that the user has to mix the liquid finished formulation of ethofumesate + phenmedipham [tradename: ®BETANAL-TA DEM, manufactured by Schering AG an emulsion concentrate (EC) containing 94 g/1 of ethofumesate and 97 g/1 of phenmedipham] or ethofumesate + phenmedipham + desmedipham [tradename: eBETANAL-PROGRESS , manufactured by Schering AG, an emulsion concentrate (EC) containing 128 g/1 of ethofumesate, 62 g/1 of phenmedipham and 16 g/1 of desmedipham] and the solid metamitron preparation [tradename: *GOLTIX, manufactured by Bayer AG; WG, 70 %] when making up the spray mixture.
In the same year there was further reported by a Hungarian author (P. Karoly) that combinations of the known herbicides phenmedipham, ethofumesate and metamitron in tank-mix applications were used successfully for weed control in sugar beet, and that a certain synergistic effect was observed. As to the fundamental disadvantages of such tank-mixes , the same considerations apply as mentioned above.
A finished formulation with a combination of these active compounds would therefore be advantageous for the user. However, it was not known to date in which manner such finished preparations can be structured since particular problems were to be expected regarding the relatively low melting point of ethofumesate and the incorporation of liquid additives, which might be necessary.
Surprisingly, finished formulations containing the technical-grade active compounds metamitron and ethofumesate and (A) phenmedipham (III) and (B) phenmedipham (III) and desmedipham (IV) or (C) desmedipham ( IV) , were now successfully prepared. Solid combination preparations could be prepared, in some cases, using liquid emulsifiers. Particularly advantageous for agricultural practice are the new finished formulations in the form of water-dispersible granules ( G) .
The invention therefore relates to new herbicidal agents in the form of finished formulations, containing a combination of the active compounds metamitron (I) and ethofumesate (II) and (A) phenmedipham (III) or (B) phenmedipham (III) and desmedipham (IV) or (C) desmedipham (IV), preferably in solid form such as water-dispersible powders (WP), or in the form of water-dispersible granules (WG) , as a mixture with formulation auxiliaries, the ratio by weight of the active compounds Le A 27 649 - 2 (I) : (II) : (III) according to the combination (A) being (l)t(0.05 to 1):(0.05 to 1), preferably (1):(0.1 to 0.4): (0.1 to 0.4), and particularly preferably (l):(0.1 to 0.35): (0.1 to 0.3) , and the ratio by weight of the active substances (I) : (II) : (III) : (IV) according to combination (B) being (1):(0.05 to 1):(0.05 to 1):(0.05 to 1), preferably (1):(0.1 to 0.4): (0.1 to 0.4): (0.1 to 0.4), and particularly preferably (1):(0.1 to 0.4): (0.1 to 0.35) : (0.1 to 0.25) , the ratio by weight of the active compounds ( I ) : ( II ) : ( IV) according to combination (C) being (1):(0.05 to 1):(0.05 to 1), preferably (1):(0.1 to 0.4): (0.1 to 0.4), and particularly preferably ( 1) : ( 0.1 to 0.4): (0.1 to 0.3), the total active substance compound, both in the case of combination (A), that is to say (l) + (II) + (III) and for the combinations (B) , that is to say (I) + (II)+(III)+ (IV) , and (C), that is to say (I) + (II) + (IV) being between 20 and 75 % by weight, preferably between 30 and 70 % by weight .
Preferred solid formulations are formulations such as water-dispersible powders (WP) and water-dispersible granules (WG) . Particularly preferred solid formulations are water-dispersible granules.
As has been found, the WP formulations can be prepared in a surprisingly simple manner by mixing the active compounds with the formulation auxiliaries suitable for a WP formulation in the abovementioned ratio by weight, grinding the mixture (for example using a customary air- Le A 27 649 - 3 - jet mill), followed by homogenising by remixing.
The G formulations are obtained by (a) first preparing a premix from the active compounds (I), (II) and (III) or (I), (II)/ (HI) and (IV) or (I), (II) and (IV) - in the abovementioned ratios by weight - and the formulation auxiliaries which are suitable for a WG formulation by mixing, grinding (expediently using a customary air-jet mill), followed by remixing, (b) then treating this premix with water in a fluidised- bed granulator in a customary manner, followed by drying at an inlet air temperature of 50-90°C to a product temperature of 30-60°C, and (c) separating the desired granules (having particle sizes between 200 and 1500 /.m) by sieving, the too small particles (<200 /.m) and the too large particles (>1500 μΐα) being separated off.
As has furthermore been found, a particular - continuous - embodiment of the last-described process for the preparation of the WG formulations according to the invention consists in preparing a highly-concentrated suspension from the premix described above under (a) by adding about the same amount by weight of water with vigorous Le A 27 649 - 4 - stirring, then feeding this suspension to a special granulation apparatus (as described in the - corresponding - patent documents EP-A-0,163,863 or DE-A1-3,413,200) and continuously discharging the product formed, at a product temperature of 30-60eC and an inlet air temperature of about 100-125°C.
The resulting product which, by virtue of the apparatus, is highly uniform (granules having a particle size of about 500 μτα) needs no further sieving.
Each of the active compounds are employed in the form of the technical-grade active compounds, for which the following melting points (m.p.) were determined: metamitron (I) - m.p. 166°C [= 3-methyl-4-amino-6-phenyl-l,2 , 4-triazin-5 ( 4H) - one] ; ethofumesate (II) - m.p. 69 °C [= 2-ethoxy-2, 3-dihydro-3, 3-dimethyl-5-benzofuranyl methanesulfonate] ; phenmedipham (III) - m.p. 144 °C [ = 3-methoxycarbonylaminophenyl-N- ( 3 ' -methylphenyl ) - carbamate] .
Le A 27 649 - 5 - desmedipham (IV) - m.p. 120°C [= 3-ethoxycarbonylaminophenyl-N-phenyl-carbamate] .
All the relevant technical data of the active compounds can be seen from the specialist literature [cf., for example, The Pesticide Manual, 8th ed., published by The British Crop Protection Council, 1987, pages 353-354 in the case of (II), page 536 in the case of (I) , pages 652-653 in the case of (III) and pages 242-243 in the case of (IV) ] .
The formulation auxiliaries required are certain carriers, dispersants and, if necessary, certain emulsifiers or wetting agents .
Suitable carriers are ground synthetic minerals such as aluminium oxide, silicates or silicic acids in connection with ground natural minerals such as kaolins, clays, quartz or attapulgite. In the case of the silicic acids, absorption or precipitation silicic acids have proved particularly useful.
Preferred dispersing agents used are ligninsulphonates or alkylaryl sulphonates.
Preferred emulsifiers which were used and which were effective as additives were polyoxyethylene alkyl ethers, silicone surfactants or polyols, and examples of wetting agents which can be used are condensation products of ethylene oxide with phenol. Condensation products of Le A 27 649 - 6 - ethylene oxide with phenol can also be used as emulsifiers .
All formulation auxiliaries mentioned are commercially available products .
The WP formulations according to the invention (combination (A) or (C)) preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethofumesate (II)/ 0.1 - 0.4 parts by weight of phenmedipham (III), or 0.1 - 0.4 parts by weight of desmedipham (IV), 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin.
The WP formulations according to the invention (combination (A) ) particularly preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.35 parts by weight of ethofumesate (II), 0.1 - 0.3 parts by weight of phenmedipham (III), 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, Le A 27 649 - 7 - 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin.
The WP formulations according to the invention (combination (C)) particularly preferably have the following composition: per part by weight of metamitron ( I ) : 0.1 - 0.4 parts by weight of ethofumesate (II), 0.1 - 0.3 parts by weight of desmedipham (IV), 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin.
The WP formulations according to the invention (combination (B)) preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethofumesate (II), 0.1 - 0.4 parts by weight of phenmedipham (III), 0.1 - 0.4 parts by weight of desmedipham (IV), 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin.
Le A 27 649 - 8 - The WP formulations according to the invention (combination (B)) particularly preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethofumesate (II), 0.1 - 0.35 parts by weight of phenmedipham (III), 0.1 - 0.25 parts by weight of desmedipham (IV), 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin.
The WG formulations according to the invention (combination (A) or (C)) preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethofumesate (I), 0.1 - 0.4 parts by weight of phenmedipham (III), or 0.1 - 0.4 parts by weight of desmedipham (IV), 0.2 - 0.5 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.1 - 0.3 parts by weight of silica and 0.0 - 0.2 parts by weight of kaolin.
The WG formulations according to the invention (combination (A) ) particularly preferably have the following composition: Le A 27 649 - 9 - per part by weight of metamitron (I): 0.1 - 0.35 parts by weight of ethofumesate (II), 0.1 - 0.3 parts by weight of phenmedipham (III), 0.2 - 0.5 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.1 - 0.3 parts by weight of silica and 0.0 - 0.2 parts by weight of kaolin.
The WG formulations according to the invention (combination (C)) particularly preferably have the following composition: per part by weight of metamitron ( I ) : 0.1 - 0.4 parts by weight of ethofumesate (II), 0.1 - 0.3 parts by weight of desmedipham (IV), 0.2 - 0.5 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.1 - 0.3 parts by weight of silica and 0.0 - 0.2 parts by weight of kaolin.
The WG formulations according to the invention (combination (B)) preferably have the following composition: per part by weight of metamitron (I): 0. 1 - 0. 4 parts by weight of ethofumesate 0. 1 - 0. 4 parts by weight of phenmedipham (HI)/ 0. 1 - 0. 4 parts by weight of desmedipham (IV), 0. 2 - 0. 5 parts by weight of dispersant, 0. 0 - o.. 3 parts by weight of emulsifier , 0. 1 - 0. 3 parts by weight of silica and Le A 27 649 - 10 - 0.0 - 0.2 parts by weight of kaolin.
The G formulations according to the invention (combination (B)) particularly preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethofumesate (II)/ 0.1 - 0.35 parts by weight of phenmedipham (III), 0.1 - 0.25 parts by weight of desmedipham (IV), 0.2 - 0.5 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.1 - 0.3 parts by weight of silica and 0.0 - 0.2 parts by weight of kaolin.
For further details, reference is made to the preparation examples .
Bearing in mind the basic technical problems which had to be overcome in the preparation of the new solid finished formulations, especially the water-dispersible granules, the results achieved must be considered as surprising: The preparation of a ground mixture of the active compound ethofumesate usually presents difficulties because of the low melting point of about 69 °C. In an air-jet mill, this results in blocked jets or caking in the grinding chamber. To date, the active compound has only been marketed in the form of a liquid formulation. However, in the mixtures described herein, the active Le A 27 649 - 11 - compound ethofumesate in the combinations (A), (B) and (C) can be ground without problems. Above all, the grindability of the herbicide mixture is also retained when, in addition to the active compounds, a liquid emulsifier is used in the formulation, up to a content of about 10 %.
In general, granulation of an active compound having a low melting point presents problems. Surprisingly, however, the premix with the active substances can be granulated without particular problems. Surprisingly, the premix can also be granulated when it contains a liquid emulsifier.
The granules obtained redisperse completely, even though up to about 10 % of highly-disperse silica are incorporated. This silica component usually does not completely redisperse after granulation.
Surprisingly, the same premix can be granulated by the customary processes, preferably in a powder process such as, for example, fluidised-bed granulation, or in a so-called slurry process, for example, spray drying. ("Slurry" means "concentrated aqueous suspension").
Surprisingly, the (pre)mixture can also be ground and, if desired, subsequently granulated when the liquid emulsifier and the active compound metamitron (I) have previously been molten together at 160 °C without degradation of active compound.
Le A 27 649 - 12 - Furthermore, it has been found that the finished formulations according to the invention, in particular the new G formulations, are outstandingly suitable for selective combating of weeds , in particular in beet cultures .
The new finished formulations prove to be high-quality preparations which meet the requirements of practice and have a broad range of activity, for combating dicotyledon and monocotyledon harmful plants including problem weeds such as Mercurialis annua and Galium aparine in beet cultures.
Surprisingly, it has emerged in corresponding comparison trials that the WG formulations according to the invention are superior to the known tank mixes in some cases as regards their action and in some cases as regards their compatibility, and hence have additional advantages compared with the prior art.
Moreover, the new finished formulations can also be employed as selective herbicides in cultures of Beta beets, strawberries, mangel-wurzel, spinach and other fruit and vegetable cultures.
Other typical weeds which may be mentioned which can occur in the abovementioned cultures and which can be combated successfully with the agents according to the invention are the following: Dicotyledon weeds of the genera; Sinapis, Lepidium, Le A 27 649 - 13 - Stellaria, Matricaria/ Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeop-sis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
The application rates of active compound correspond to the amounts of active compound applied in practice when the previously known tank mixes are used, in each case based on the same unit area.
It is particularly important for the user in agricultural practice that the new WG formulations have substantial technical advantages compared with other formulations of the same active compounds : for example, packaging is simpler (can be emptied without leaving residues and hence disposed of without problems, while the amount of packaging material is considerably reduced) ; the granules can be measured by volume, and there is no dust formation or splashing of the concentrate Le A 27 649 - 14 - when the spray mixtures are made up; the new solid formulations are completely free from solvents compared with the known emulsion concentrates (EC) .
The action of a leaf-acting herbicidal agent can be increased by adding an emulsifier. Such an additive is customarily added in large amounts in a tank mix. Surprisingly, only a small amount of about 5-10 % of the emulsifier used in the finished formulation according to the invention is sufficient for obtaining an increase of action of the preparations described herein.
The preparation and use examples which follow are intended to further illustrate the invention.
A) Preparation Examples Examples of the preparation of the G finished formula-tions according to the invention of metamitron & etho-fumesate & phenmedipham .
A premixture was prepared from the components listed in Table 1 below by mixing, grinding the mixture in an air-jet mill, followed by remixing.
Each of these premixtures was treated with water in a fluidised-bed granulator manufactured by Aeromatik (Strea 1) in the customary manner and subsequently dried to a product temperature of 40 °C at an inlet air temperature of 68°C. The too small particles (<200 μτα) and the Le A 27 649 - 15 - too large particles (>1500 μΐτι) were subsequently sieved off from the product obtained.
When the formulations WG-3, WG-5 and WG-7 were prepared, a suspension was prepared in each case using 3.0 kg of premixture and 3.0 1 of water. This suspension was fed into an apparatus described in Patent Document DE-A-3,413,200 or EP-A-0 , 163 , 863. The product was continuously discharged at a product temperature of 40 eC and at an inlet air temperature of 110 °C. Sieving of the product obtained, granules about 500 μτα in size, was no longer necessary due to the apparatus.
In the WG formulations described in Table 1, the ratio by weight of the active compounds is (I) : (II) : (III) = 1:0.132:0.136 in the case of WG 1 to 10 (I) : (II) : (III) = 1:0.270:0.279 in the case of WG 11.
The same is also true for all use examples which follow.
Le A 27 649 - 16 - Table 1 : Composition of the WG formulations prepared Formulation Active compound1' Disper- Emulsi-No. (I) (II) (III) sant2) fier3 Sil [%] [%1 [%] [ ] [%] WG-1 50.0 6.60 6.80 20.0 0.0 5 WG-2 50.0 6.60 6.80 20.0 5.0 7 WG-3 50.0 6.60 6.80 20.0 5.0 7 WG-4 45.0 5.94 6.12 20.0 7.5 7 WG-5 45.0 5.94 6.12 20.0 7.5 7 WG-6 45.0 5.94 6.12 20.0 10.0 10 WG-7 45.0 5.94 6.12 20.0 10.0 10 WG-85' 45.0 5.94 6.12 20.0 10.0 10 WG-9 50.0 6.60 6.80 20.0 7.0 7 WG-106) 50.0 6.60 6.80 20.0 7.0 about 9 WG-11 23.3 6.30 6.50 15.0 5.0 5 Notes : 1) Active compound ( I ) metamitron, technical grade Active compound (II) ethofumesate, technical grade Active compound (III) phenmedipham, technical grade Dispersant: alkylaryl sulphonate Emulsifier: Polyoxyethylene- ( 6 ) tridecyl ether In the preparations containing an emulsifier, a 50 % premixture on silica was prepared using a customary "pulveriser" .
Carriers: highly-disperse precipitation silica + kaolin W The amount of the active compound metamitron (I) and the amount of emulsifier were molten together at about 160 °C and the melt was cooled. The waxy composition was mixed with silica. 60 % of emulsifier and 40 % of silica were employed as the premixture; this premixture was prepared by mixing the two components. Kaolin was not added.
Le A 27 649 - 18 - B) Use Examples Preparations used in the experiments ; (a) according to the prior art - tank mix/mixture comparison agent consisting of *GOLTIX/metamitron ( I ) , manufactured by Bayer AG, 70 % WG formulation; *TRAMAT/ethofumesate (II)/ manufactured by Schering AG, liquid formulation, active compound content 200 g/1; ®BETANAL/phenmedipham (III), manufactured by Schering AG, EC formulation, active compound content 157 g/1. (b) according to the invention - the WG finished formulations WG-1 to WG-10 of metamitron & ethofumesate & phenmedipham which are described in the preparation examples.
Experimental set-up; Preparing the active compound preparations: the amounts required of the formulations of the preparations are weighed or measured and made into spray mixtures using water .
Post-emergence method: test plants are grown in the greenhouse under controlled conditions (standard soil/- Le A 27 649 - 19 - normal soil, temperature, humidity, light) up to a size of 5 to 10 cm and then treated with the herbicides in a spray cabin.
The concentration of the spray mixtures is so chosen that the particular amounts of active compound desired per unit area are applied at an application rate of 500 1 of water/ha.
After the treatment, the test containers containing the test plants are kept in the greenhouse until they are evaluated. Two to three weeks after the treatment, the degree of damage to the plants is assessed as a % damage compared with untreated control plants .
The figures denote: 0 = no action/damage (like untreated control) 100 = total combating/complete damage The formulations, application rates, test plants and actions can be seen from Tables A-G which follow.
Abbreviations used in the tables: active ingredient Beta vulgaris (beet) Amaranthus retroflexus Galium aparine Matricaria inodora Mercurialis annua Polygonum convolvulus Sinapis alba Le A 27 649 - 20 - Table A-l Post-emergence test/greenhouse (standard soil) +ethofumesate +phenmedipham according to the invention; WG-2 metamitron 2000&264&272 100 I & ethofumesate & phenmedipham WG-4 metamitron 2000&264&272 90 & ethofumesate & phenmedipham WG-7 metamitron 2000&264&272 0 90 & ethofumesate & phenmedipham in the case of (b) , cf. in each case the preparation examples (a Table A-2 Post-emergence test/greenhouse (normal soil) +ethofumesate +phenmedipham according to the invention; WG-1 metamitron 500&66&68 100 & ethofumesate t t & phenmedipham WG-2 metamitron 500&66&68 10 100 & ethofumesate & phenmedipham according to the invention; WG-7 metamitron 500& 66& 68 100 & ethofumesate & phenmedipham WG-6 metamitron 500& 66&68 90 o O & ethofumesate & phenmedipham Table B Post-emergence test/greenhouse (normal soil) Formulation Application Test plants rate Damage or action g/ha in % a . i . BEAVA GALAP according to the prior art tank mix/- mixture; metamitron 1000+132+136 10 80 +ethofumesate +phenmedipham according to the invention: WG-8 metamitron 1000&132&136 10 98 & ethofumesate & phenmedxpham Table C Post-emergence test/greenhouse (standard soil) Formulation*' Application Test plants rate Damage or action g/ha in % a . l . BEAVA MATIN according to the prior art tank mix/- mixture ; metamitron 4000+528+544 20 90 +ethofumesate +phenmedipham according to the invention; WG-1 metamitron 4000&528&544 10 100 & ethofumesate & phenmedipham according to the prior art tank mix/- mixture; metamitron 4000+528+544 20 90 +ethofumesate +phenmedipham (b) according to to the inventions WG-3 metamitron 4000&528&544 0 90 & ethofumesate & phenmedipham +phenmedipham according to the invention; WG-5 metamitron 4000&528&544 90 & ethofumesate & phenmedipham G-6 metamitron 4000&528&544 10 100 & ethofumesate & phenmedipham Table E-2 Post-emergence test/greenhouse (normal soil) Formulation*' Application Test plants rate Damage or action g/ha in % a.i. BEAVA POLCO according to the prior art tank mix/- mixture: metamitron 2000+264+272 10 90 +ethofumesate +phenmedipham (b) according to the invention: WG-9 metamitron 2000&264&272 100 & ethofumesate & phenmedipham WG-10 metamitron 2000&264&272 100 & ethofumesate & phenmedipham Table F Post-emergence test/greenhouse (standard soil) Formulation* Application Test plants rate Damage or action g/ha in % a . i . BEAVA SINAL according to the prior art tank mix/- mixture ; metamitron 4000+528+544 20 90 +ethofumesate +phenmedipham (b) according to the invention: WG-5 metamitron 4000&528&544 90 & ethofumesate & phenmedipham
Claims (1)
1. 30 98717/2 Claims Herbicidal agents in the form of solid finished formulations, containing an admixture of the active compounds metamitron (I) and ethofumesate (II) and (A) phenmedipham (III) or (B) phenmedipham (III) and desmedipham (IV) or (C) desmedipham (IV) , in a mixture with formulation auxiliaries, the ratio by weight of the active compounds (I) : (II) : (III) according to admixture (A) being (I): (0.05 to 1):(0.05 to 1), the ratio by weight of the active compounds (I) : (II) : (III) : (IV) according to admixture (B) being (1):(0.05 to 1):(0.05 to 1):(0.05 to 1) and the - ratio by weight of the active compounds (I) : (II) : (IV) according to admixture (C) being (1) : (0.05 to 1) : (0.05 to 1) , and the total active compound content in the admixture (A) , (B) and (C) being between 20 and 75 % by weight. Herbicidal agents according to Claim 1, the ratio by weight of the active compounds (I) : (II) : (III) being (1):(0.1 to 0.4): (0.1 to 0.4), of the active compounds (I) : (II) : (III) : (IV) being (1): (0.1 to 98717/2 31 0.4): (0.1 to 0.4): (0.1 to 0.4), and of the active compounds (I) : (II) : (IV) being (1): (0.1 to 0.4): (0.1 to 0.4) . Herbicidal agents according to Claim 1, the ratio by weight of the active compounds (I) : (II) : (III) being (1) : (0.1 to 0.35) : (0.1 to 0.3) , of the active compounds (I) : (II) : (III) : (IV) being (1):(0.1 to 0.4): (0.1 to 0.35): (0.1 to 0.25), and of the active compounds (I) : (II) : (IV) being (1):(0.1 to 0.4): (0.1 to 0.3). Herbicidal agents according to Claim l, the total active compound content in the admixtures (A) , (B) and (C) being between 30 and 70 % by weight relative to the total weight of the formulation. Solid finished formulations according to Claim 1, carriers, dispersants and, if appropriate, an emulsifier and/or a wetting agent being employed as formulation auxiliaries . Solid finished formulations according to Claim l in the form of water-dispersible granules. Solid finished formulations according to Claim 1 in the form of water-dispersible powders. 98717/2 Solid finished formulations according to Claims 1 and 7 in the form of water-dispersible powders ( P)/ the following formulation auxiliaries additionally being employed per part by weight of metamitron (I): 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.0 - 0.1 parts by weight of wetting agent, 0.1 - 0.3 parts by weight of silica and 0.05 - 0.2 parts by weight of kaolin. Solid finished formulations according to Claims 1 and 6 in the form of water-dispersible granules (WG) , the following formulation auxiliaries additionally being employed per part by weight of metamitron (I): 0.2 - 0.5 parts by weight of dispersant, 0.0 - 0.3 parts by weight of emulsifier, 0.1 - 0.3 parts by weight of silica and 0.0 - 0.2 parts by weight of kaolin. Process for the preparation of finished formulations in solid form according to Claim 1, in which WP (water-dispersible powder) formulations are obtained when the active compounds are mixed with the formulation auxiliaries following the ratio by weight indicated in Claim 1, and the mixture is ground and subsequently homogenised by remixing, or in which the WG (water-dispersible granules) formulations are obtained by 27 649 - 32 - 98717/2 33 (a) first preparing a premix from the active compounds (I) , (II) and (III) or (I) , (II) , (III) and (IV) or (I), (II) and (IV) - according to the ratios by weight given in Claim 1 - and formulation auxiliaries selected from carriers, dispersants and, if necessary, emulsifiers or wetting agents by mixing, grinding, followed by remixing, (b) then treating this premix with water in a fluidised-bed granulator in a customary manner, followed by drying at an inlet air temperature of 50-90 °C to a product temperature of 30-60 °C, and (c) separating the desired granules (having particle sizes between 200 and 1500 μτα) by sieving, the too small particles (<200 μπι) and the too large particles (>1500 μπι) being separated off. 11. Use of the solid finished formulations according to Claims 1 - 9 as herbicides. 12. Use of the solid finished formulations according to Claim 11 as selective beet herbicides. 13. Herbicidal agent in the form of a finished formulation according to Claim 1, substantially as hereinbefore described in any one of the Preparation Examples. For the Applicants DR. REINHOLD C0HN--AND PARTNERS Αί·ί~
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4021604 | 1990-07-06 | ||
| DE4114801A DE4114801A1 (en) | 1990-07-06 | 1991-05-07 | HERBICIDES BASED ON A COMBINATION OF METAMITRON / ETHOFUMESATE / PHENMEDIPHAM / DESMEDIPHAM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL98717A0 IL98717A0 (en) | 1992-07-15 |
| IL98717A true IL98717A (en) | 1995-08-31 |
Family
ID=25894790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL9871791A IL98717A (en) | 1990-07-06 | 1991-07-03 | Herbicidal agents based on a combination of metamitron/ethofumesate/phenmedipham/desmedipham |
Country Status (24)
| Country | Link |
|---|---|
| EP (1) | EP0465899B1 (en) |
| AT (1) | ATE126418T1 (en) |
| BG (1) | BG60843B1 (en) |
| CZ (1) | CZ285095B6 (en) |
| DE (2) | DE4114801A1 (en) |
| DK (2) | DK0465899T3 (en) |
| ES (1) | ES2075271T3 (en) |
| FI (1) | FI102029B1 (en) |
| FR (1) | FR2664131A1 (en) |
| GB (1) | GB2245494B (en) |
| GR (1) | GR3017150T3 (en) |
| HR (1) | HRP940478B1 (en) |
| HU (1) | HU213725B (en) |
| IE (1) | IE67063B1 (en) |
| IL (1) | IL98717A (en) |
| IT (1) | IT1248515B (en) |
| MA (1) | MA22206A1 (en) |
| PL (1) | PL167920B1 (en) |
| RO (1) | RO113704B1 (en) |
| SI (1) | SI9111195B (en) |
| SK (1) | SK281281B6 (en) |
| TN (1) | TNSN91054A1 (en) |
| TR (1) | TR26935A (en) |
| YU (1) | YU48207B (en) |
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| FI93416C (en) * | 1991-09-27 | 1995-04-10 | Kemira Oy | Process for the preparation of a herbicide product in granular or tablet form |
| US5651975A (en) * | 1991-09-27 | 1997-07-29 | Harju-Jeanty; Pontus | Method for the preparation of herbicidal granular products comprising two separate phases |
| US5224428A (en) * | 1991-10-31 | 1993-07-06 | Wronkiewicz Robert D | Strengthened structure for a steering arm assembly having a compound radial fillet at juncture |
| ZA93394B (en) * | 1992-01-24 | 1993-08-05 | Ici Australia Operations | Water dispersible granules of low melting point pesticides. |
| TR28994A (en) * | 1993-03-19 | 1997-07-21 | Kemira Oy | A method for obtaining herbicide (herbicide) granular products. |
| DE4329974A1 (en) * | 1993-09-04 | 1995-03-09 | Stefes Pflanzenschutz Gmbh | Aqueous herbicidal suspension concentrates |
| DE19814092A1 (en) * | 1997-04-15 | 1998-10-22 | Stefes Agro Gmbh | Herbicidal, fungicidal and insecticidal compositions |
| RU2263449C1 (en) * | 2004-05-06 | 2005-11-10 | Закрытое акционерное общество "Щелково Агрохим" | Herbicide composition |
| WO2008031445A1 (en) * | 2006-09-14 | 2008-03-20 | Cera Chem S.A.R.L. | Herbicide mixtures with improved activity, stability and pourability for use in beta-beet crops |
| CN110081627B (en) | 2011-06-13 | 2022-05-10 | 阿雷斯科技术有限公司 | Refrigeration system and method for refrigeration |
| RU2017112546A (en) | 2011-06-13 | 2019-01-25 | Ареско Текнолоджиз, Ллс | CONDENSER EVAPORATION SYSTEM AND METHOD OF OPERATION |
| CN103734144B (en) * | 2013-12-30 | 2015-12-30 | 浙江中山化工集团股份有限公司 | A kind of beet ground complex weedicide and preparation method thereof |
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| DE2413262A1 (en) * | 1974-03-20 | 1975-09-25 | Bayer Ag | Means for selective weed control in turnips |
| ES8604495A1 (en) * | 1983-09-20 | 1986-02-01 | Koege Kemisk Vaerk | A process for the preparation of known herbicidally active phenyl carbamates. |
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1991
- 1991-05-07 DE DE4114801A patent/DE4114801A1/en not_active Withdrawn
- 1991-06-13 RO RO147779A patent/RO113704B1/en unknown
- 1991-06-20 IT ITMI911703A patent/IT1248515B/en active IP Right Grant
- 1991-06-22 EP EP91110322A patent/EP0465899B1/en not_active Expired - Lifetime
- 1991-06-22 AT AT91110322T patent/ATE126418T1/en not_active IP Right Cessation
- 1991-06-22 DK DK91110322.4T patent/DK0465899T3/en active
- 1991-06-22 DE DE59106258T patent/DE59106258D1/en not_active Expired - Lifetime
- 1991-06-22 ES ES91110322T patent/ES2075271T3/en not_active Expired - Lifetime
- 1991-06-27 CZ CS911968A patent/CZ285095B6/en not_active IP Right Cessation
- 1991-06-27 SK SK1968-91A patent/SK281281B6/en unknown
- 1991-07-02 GB GB9114249A patent/GB2245494B/en not_active Revoked
- 1991-07-03 TR TR00673/91A patent/TR26935A/en unknown
- 1991-07-03 IL IL9871791A patent/IL98717A/en not_active IP Right Cessation
- 1991-07-04 BG BG94756A patent/BG60843B1/en unknown
- 1991-07-04 FI FI913254A patent/FI102029B1/en active IP Right Grant
- 1991-07-04 PL PL91290937A patent/PL167920B1/en unknown
- 1991-07-05 YU YU119591A patent/YU48207B/en unknown
- 1991-07-05 FR FR9108490A patent/FR2664131A1/en not_active Withdrawn
- 1991-07-05 HU HU912281A patent/HU213725B/en not_active IP Right Cessation
- 1991-07-05 MA MA22479A patent/MA22206A1/en unknown
- 1991-07-05 TN TNTNSN91054A patent/TNSN91054A1/en unknown
- 1991-07-05 SI SI9111195A patent/SI9111195B/en unknown
- 1991-07-05 DK DK131491A patent/DK131491A/en not_active Application Discontinuation
- 1991-07-05 IE IE235991A patent/IE67063B1/en not_active IP Right Cessation
-
1994
- 1994-08-23 HR HRP-1195/91A patent/HRP940478B1/en not_active IP Right Cessation
-
1995
- 1995-08-17 GR GR950402112T patent/GR3017150T3/en unknown
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| Date | Code | Title | Description |
|---|---|---|---|
| RH | Patent void |