IE67063B1 - 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
- IE67063B1 IE67063B1 IE235991A IE235991A IE67063B1 IE 67063 B1 IE67063 B1 IE 67063B1 IE 235991 A IE235991 A IE 235991A IE 235991 A IE235991 A IE 235991A IE 67063 B1 IE67063 B1 IE 67063B1
- Authority
- IE
- Ireland
- Prior art keywords
- weight
- parts
- active compounds
- iii
- formulations
- 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 41
- 239000005579 Metamitron Substances 0.000 title claims abstract description 32
- 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 32
- 239000005594 Phenmedipham Substances 0.000 title claims abstract description 29
- 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 28
- 239000005512 Ethofumesate Substances 0.000 title claims abstract description 27
- 239000004009 herbicide Substances 0.000 title claims abstract description 16
- 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 abstract description 14
- 239000005503 Desmedipham Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 113
- 238000009472 formulation Methods 0.000 claims abstract description 73
- 239000004562 water dispersible granule Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 26
- 241000335053 Beta vulgaris Species 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 235000016068 Berberis vulgaris Nutrition 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000003995 emulsifying agent Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 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
- 239000002245 particle Substances 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 6
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 description 20
- 239000002689 soil Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- -1 uranyl methanesulphonate Chemical compound 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
- 125000005624 silicic acid group Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 244000192528 Chrysanthemum parthenium Species 0.000 description 2
- 241000207892 Convolvulus Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241001101998 Galium Species 0.000 description 2
- 241000209510 Liliopsida Species 0.000 description 2
- 235000017945 Matricaria Nutrition 0.000 description 2
- 235000007232 Matricaria chamomilla Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 241000219295 Portulaca Species 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
- 150000002500 ions Chemical class 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 1
- 241001519451 Abramis brama Species 0.000 description 1
- 241000219144 Abutilon Species 0.000 description 1
- 241000209136 Agropyron Species 0.000 description 1
- 241000743985 Alopecurus Species 0.000 description 1
- 241000404028 Anthemis Species 0.000 description 1
- 241001666377 Apera Species 0.000 description 1
- 244000293889 Bombax malabaricum Species 0.000 description 1
- 235000004480 Bombax malabaricum Nutrition 0.000 description 1
- 241000611157 Brachiaria Species 0.000 description 1
- 235000006463 Brassica alba Nutrition 0.000 description 1
- 244000140786 Brassica hirta Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000320316 Carduus Species 0.000 description 1
- 235000000509 Chenopodium ambrosioides Nutrition 0.000 description 1
- 244000098897 Chenopodium botrys Species 0.000 description 1
- 235000005490 Chenopodium botrys Nutrition 0.000 description 1
- 241000132536 Cirsium Species 0.000 description 1
- 241000320605 Dactyloctenium Species 0.000 description 1
- 241000208296 Datura Species 0.000 description 1
- 235000017896 Digitaria Nutrition 0.000 description 1
- 241001303487 Digitaria <clam> Species 0.000 description 1
- 235000007351 Eleusine Nutrition 0.000 description 1
- 241000209215 Eleusine Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000234642 Festuca Species 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 241000816457 Galeopsis Species 0.000 description 1
- 241000748465 Galinsoga Species 0.000 description 1
- 241000550087 Lanium Species 0.000 description 1
- 241000064140 Lindernia Species 0.000 description 1
- 235000021534 Mangelwurzel Nutrition 0.000 description 1
- 241000221024 Mercurialis Species 0.000 description 1
- 235000011096 Papaver Nutrition 0.000 description 1
- 240000001090 Papaver somniferum Species 0.000 description 1
- 241000209048 Poa Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000218206 Ranunculus Species 0.000 description 1
- 101100001518 Rattus norvegicus Igfals gene Proteins 0.000 description 1
- 241000490453 Rorippa Species 0.000 description 1
- 240000009132 Sagittaria sagittifolia Species 0.000 description 1
- 241000780602 Senecio Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 235000005775 Setaria Nutrition 0.000 description 1
- 241000232088 Setaria <nematode> Species 0.000 description 1
- 241000207763 Solanum Species 0.000 description 1
- 235000002634 Solanum Nutrition 0.000 description 1
- 241000488874 Sonchus Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 244000273618 Sphenoclea zeylanica Species 0.000 description 1
- 235000017967 Sphenoclea zeylanica Nutrition 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 240000006694 Stellaria media Species 0.000 description 1
- 241000245665 Taraxacum Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 241000219422 Urtica Species 0.000 description 1
- 240000005592 Veronica officinalis Species 0.000 description 1
- 241000405217 Viola <butterfly> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000016087 ovulation Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
Th© Invention relates to new solid finished formulations of the known berbicidal active substances aetaaitron + ethofuaesate + (A) phenaedipham, or (3, phenaediphaa » desaediphaa or (C) desaediphaa, preferably solid foraala5 tions such as water-dispersible powders (WP) aad water- f dispersible granules (WG),- and their use as herbicides, ia particular as selective beet herbicides» Mixtures of these active compounds have previously been, described, ditto tank mixes of a finished formulation of ©thofuaesate + phenmediphaa with aet&aitron (cf.
J. Marshall et al, 1987, British Crop Protection Conference Weeds (1), page 233-240), which have proved suitable xa practice for selective combating of weeds In beet cultures. However, the disadvantage of these tank IS misses Is that the user has to mix the liquid finished formulation of ethofuaesate + phenaediphaa [tradename: ®3ΞΤΑίϊΑΙι-ΤΑ2Κ)ΞΜ, manufactured by Sobering AG; an emulsion concentrate (BC) containing 94 g/1 of ethofuaesate and 97 g/1 of phenaediphaa] or ©thofuaesate + phanaediphaa * desaediphaa [tradename: ®BSTAJ9AI»-PROGRESS, manufactured by Sobering AG, an emulsion concentrate (SC) containing 128 g/1 of ©thofuaesate, S2 g/1 of pheaaediphaa and XS g/1 of desaediphaa] and the solid aetaaitron preparation, [tradename: *GOX>TXX, manufactured by Bayer AG; WG, 70 %) when making up the spray mixture.
A solid finished formulation with a combination of these active compounds would therefore he advantageous for the user. However, it vas not known to date la which aaaax such solid finished preparations can he structured since particular problems were to he expected regarding the relatively low melting point of ©thofuaesate and th© incorporation of liquid additives, which might be necessaryA Surprisingly, solid finished formulations containing th© technical-grade- active compounds aeteaitron and ethofuaesat® and (A) phenmedipham (III) and (B) phenmedlpham (XII) and desmedlpham (IV) ox (C) desmedipham (XV) , were now successfully prepared. Solid combination. prepar5 at ions could b>® prepared, ia seme cases, using liquid ossulsifiers. Particularly advantageous for agricultural practice are the aew solid finished fovulations in the tors of water-dispersible granules (WG).
Th® invention therefore relates to new herbicidal agents In the form of solid finished formulations, containing a combination of the active compounds metamitron (I) and ethofuxaesate (II) and (A) phenmedipham (III) or (3) phenmedipham (III) aad desmedipham (IV) or (C) de smedipham (IV), preferably in the form of water-dispersible powders (WP), or la the form of water-dispersible granules (WG), as a mixture with formulation auxiliaries, the ratio by weight of the active compounds (I):(II):(III) according to combination (A) 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 (X) :(0.1 to 0.35):(0.1 to 0.3), and the ratio by weight of the active compounds (I):(II):(III):(IV) according to combination (3) 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), and the total active compound content, both in the case of combination (A), that is to say (1) + (11)-^(III) and for the combinations (3), 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. - 3 Preferred solid formulations are water-dispersible powders As has been found, the WP formulations cat be prepared ia a surprisingly simple manner by mixing the active compounds with the formulation auxiliaries suitable for a W formulation in the abovementioned ratio by weight, grinding the mixture (for example using a customary airjet mill), followed by homogenising by remixing.
The WG formulations are obtained by (a) first preparing a prefix from the active compounds (2), (22) and (III) or (ϊ),» (II), (121) and (IV) or (2) g, (22) 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 premise with water ia a fluidisedbed 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 pm) by sieving, the too small particles (<200 μ») aad the too large particles (>1500 Jim) being separated off.
As has furthermore been found, a particular - continuous - eiabodiment 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 aaouat by weight os water with vigorous stirring, then feeding this suspension to a special granulation apparatus (as described in the - correspoafi5 ing - patent documents HS’-A-O,163,853 or DB-A1-3,413,200) and continuously discharging the product formed, at a product temperature of 30-60®C and as inlet air teaperature of about 100-125®C.
The resulting product which, by virtue of the apparatus, is highly uaifosa (granules having a particle size of about 500 pir) needs no further sieving.
Saca of the active compounds are employed ia the form of the technical-grade active compounds, for which the following melting points (m.p.) were determined: metsuoitron (I) - m.p. 1SS®C [= 3-saethyl-4-0aaiao-5-phenyl-l, 2,4-triazxn-5 (4H) one] s ethofumesate (11) - m.p. 6&°C [s 2-ethoxy-2,3-dihyfiro-3,3-dimethyl-5-beazof uranyl methanesulphonate] ? phenmedipham (IXX) - m.p. 144°C S> 3-methoxycarbonylamxaophenyl Hi- <3-methylphenyl) carbamate]. desssedipham (XV) - m.p. 120°C [" 3~«thoscyc&rbonyla3si.Siophenyl-S3-pb.enylcarbasaafce3 · All the relevant technical data of the active compounds caa be seea from the specialist literature [cf., for example. The Pesticide 'Manual, 8th ed., published by Th® British Crop Protection Council, 1987, pages 353-354 in the ease of (XX), page 536 in the case of (1), pages 652-653 i» the. esse of (XII) aad pages 242-243 ia the case of (XV)3The formulation auxiliaries required are certain carriers, dispersants and, if appropriate, certain emulsi5 tiers or wetting agents.
Suitable carriers are ground synthetic minerals such as aluminium oxide, silicates or silicic acids in connect ion with ground natural minerals such as kaolins, clays, quarts or attapulgite. In the case of the silicic acids, absorption or precipitation silicic acids have proved particularly useful.
Preferred dispersing agents used are lignisusulphonates 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 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 composi25 tions per part by weight of mataaitroa (I) ; 0.1 - 0.4 parts by weight of ethofusiesate (II), 0.1 - 0.4 parts by weight of pheamedipfesm (III), or 0.1 - 0.4 parts by weight of desmediphem (IV,. 0.05 - 0.2 parts by weight of dispersant, 0.0 - 0.3 parts by weight of easulsifier, 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 formulations according to the invention (combination (A)) particularly preferably have the following composition: per part by weight of saefcasaitron (I); 0.1 - 0.35 parts by weight of ©thofuaesat© (II), 0,1 - 0.3 parts by weight of phenmediphasa (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, 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 (comhin15 ation (C)) particularly preferably have the following compositions per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ©thofumesate (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 (3)) preferably have the following compositions per part by weight of metamitron (I)s 0.1 - 0.4 parts by weight of ethofumesate (ID, 0.1 - 0.4 parts by weight of phenmedipham (HI) , 30 0.1 - 0.4 parts by weight of de smedipham (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 o£ silica and 0.05 - 0-2 parts by weight of kaolin.
The W formulations according to the invention (combination (3)) particularly preferably have the following composition: per part by weight of metamitron (I): 0.1 - 0.4 parts by weight of ethoraaaesate (Π), 0.1 - 0.35 parts by weight of pheasaedipham (XXX), 0.1 - 0.25 parts by weight of deenediphem (XV), 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 compositions per part by weight of saetaraitroa (X) : 0.1 - 0.4 parts by weight of ethofumesate (X), 0.1 - 0.4 parts by weight of phenxaedipham (XXX), 0.1 - 0.4 parts by weight of de smedipham (XV), 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 (coaCbxnation (A)) particularly preferably have the following composition: per parts by weight of metasitron (I) : 0.1 - 0.35 parts by weight of ethofumesate (XI), 0.1 - 0.3 parts by weight of phesmedipha»' (XIX), 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 parts 0.1 - 0.4 0.1 - 0.3 0.2 ~ 0.5 0.0 - 0.3 0.1 ~ 0.3 0.0 - 0.2 by weight of metasaitroa (X> s parts by weight of ©thofusaesat© (21), parts by weight of de smedxphasa (IV), parts by weight of dispersant, parts by weight of emulsifier. parts by weight of silica and parts by weight of kaolin.
Th© WG formulations according to the invention (combination (3)) preferably have the following composition: per parts by weight of aaetamitron (1) : 0.1 - 0.4 parts by weight of ethofumesate (ID, 0.1 - 0.4 parts by weight of pheamediphasa (III) 0.1 - 0.4 parts by weight of desmedipban (Tv), 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 th© invention (combination (3)) particularly preferably have the following composition: per parts by weight of met asd.tr on (I) : 0.1 - 0.4 parts by weight of ethofwnesate (II),» 0.1 - 0.35 parts by weight of phemaediphaa (III), 0.1 - 0.25 parts by weight of desnediphsia (XV), 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 kaolin9 For further details, reference Is made to the preparation examples.
Bearing la mind the basic technical problems which had to be overcome in the preparation of the new solid finished soEmulations, 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 lew melting point of about 69°C. In as air-jet mill, this results la blocked jets or caking is 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 compound ethofumesate in the combinations (A), (3) and (C) caa be ground without problems. Above all, the griadability of the herbicide mixture Is also retained when, ia 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 caa be granulated without particular problems. Surprisingly, the preoaix can also be granulated when it contains a liquid emulsifier.
The granules obtained redispers© completely, even though up to about 10 % of highly-disperse silica are incorporated. This silica component usually doe© not completely redisperse after granulation.
Surprisingly, the same premiss can be granulated by the customary processes, preferably In a powder process such as, for example, fluid!sed-bed granulation, or In a socalled slurry process, for example, spray drying. ('Slurry™ means "concentrated aqueous suspension").
Surprisingly, th© (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 16Q'®C without degradation of active ccopouafi.
Furthermore, it has been found that the solid finished foxaaulatioas according to the invention, in particular th© new W formulations, are outstandingly suitable for selective combating of weeds, in particular in beet cultures.
The new solid finished formulations prove to be highquality preparations which meet th© requirements of practice .and have a broad range of activity, for combating dicotyledon and monocotyledon, harmful plants including problem weeds such as Mercurialxs annua and Galium aparia© 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 soae cases as regards their compatibility, and hence have additional advantages compared with the prior art.
Moreover, the new solid finished formulations can also to© 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 th© abovementzoned cultures and which can be combated successfully with the agents according to fhe invention are the following: Dicotyledon weeds of the genera: S inapis, Lepidiusa, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodiusa, Urtica, Senecio, Amaraathus, Portulaca, Xanthiuxa, Portulaca, XX Convolvulus, Ipcmioea, Folygoaum, Sesbania, Ambrosia, Cirsium, Carduuss, Sonchus, Solanum, Rorippa, Ratals,, Lindernia, Lanium, Veronica, Abutilon, Essex, Datura, Viola, Galeopsis, Papaver, Ceataurea, Trifolium, Ranunculus, Taraxacum.
Monocotyledon weeds of the genera; Echxnochloa, Setaria, P&aicusa, Digitaria, Bhleum, Poa, Festuca, Eleusine, Brachiaria, Dolium, Breams, Aveaa, Cyparus, Sorghum, Agropyron, Cyaodon, Moaochoria, Fimbrxstylis, Sagittaria, XO Sleocharis, Scixpus, Paspalusa, Xschaemum, Sphenoclea, Dactyloctenium, Agrrostis, Alopecurus, Apera.
The application rates of active compound correspond to the amounts of active compound applied in practice idea the previously known tank misses are used, in each case based oa th© same unit area.
Xt Is particularly important for the user In agricultural practice that th© new WG formulations have substantial technical advantages compared with other formulations of the seme «active compounds: for example, packaging Is simpler (can b© emptied without leaving residues aad hence disposed of without problems, while the amount of packaging material Is considerably reduced); th© granules can be measured by volume, and there Is not dust formation or splashing of the concentrate when the spray mixtures are made up; th© new solid formulations ar© completely free from solvents compared with th© known emulsion concentrates (EC) Th© action of a leaf-acting berbicidal agent can be increased by adding an emulsifier. Such aa 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 solid finished formulation according to th© Invention Is sufficient for obtaining aa increase of action of the preparations described herein.
The preparation and use examples which follow are intended to further illustrate the inventionA) Preparation Examples! Examples of the preparation of the W<3 finished formulations according to the invention of metamitron. & ethofumesato & phemsaediphaia.
A premixture was prepared from the components listed in Table 1 below by mixing, grinding the mixture la an airjet mill, followed by remixing.
Each of these presaixtures was treated with water la a fluifiised-bed granulator manufactured by Aeromatik (Strea 1) In the customary manner aad subsequently dried to a product temperature of 40®C at aa inlet air temperature of 68®C. The too small particles (<200 pm) and the too large particles (>1500 μη) were subsequently sieved off from the product obtained.
When the formulations WG-3, MG-5 and MG-7 were prepared, a suspension was prepared in each case using 3.0 kg of premixtur© and 3.0 1 of water. This suspension was fed Into an apparatus described In latent Document DB-A-3,413,200 or EP-A-0,163,8S3. The product was continuously discharged at a product temperature of 40°C aad at an Inlet air temperature of 110®C. Sieving of the product obtained, granules about 500 pm In sire, was no longer necessary due to the apparatus.
In the MG 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 (1):(11):(111) - 1:0.270:0.279 in the case of WG 11. - 3.3 The sane is also true for all use eaceiaples which follow Kaolin [%] Table li Composition of the WG formulations Formulation Active compound1’ Diaper- No. (I) [%] (11) [%] (111) [%1 sant E%1 WG-1 50.0 6.60 6 . @0 20.0 WG - 2 50.0 6.60 δ β 8 0 20.0 WG-3 50.0 δ - 6 0 6 . SO 20.0 WG-4 45.0 5.94 6.12 20.0 WG-5 45.0 5 ® S4 6.12 20.0 WG-6 45.0 5 e 94 6.12 20.0 WG-7 45.0 5.94 6.12 20.0 WG-85’ 45.0 5.94 6.12 20.0 WG-9 50.0 6.60 6 @0 20.0 WG-105’ 50.0 6.60 6.80 20.0 WG-11 23.3 6.30 6.50 15.0 Emulsifier" [%] Carriers4’ Silica (%] 0.0 5.0 about 11.6 5.0 7.5 about 4.10 5.0 7.5 about 4.10 7.5 7.5 about 7.94 7.5 7.5 about 7.94 10.0 10.0 about 2.94 10.0 IG . 0 about 2.94 10.0 10.0 about 2.94 7.0 7.0 about 2.60 7.0 about 9.6 0.0 5.0 5.0 38.9 O Mil (X) metamitron, technical grade (IX) ethofumesate, technical grade (XIX) =. phenmediphan, technical grade NO 2 Active compound Active compound Active compound 2) Dispersant: alkylaxyl sulphonate 3> Smulsifier: Polyoxyethylene- (5) tridecyl ether In th© preparations containing an emulsifier, a 50 % premixture on silica was prepared using a customary "pulveriser'® ., 4) Carriers: hxghly-dxsperse precipitation silica + kaolin W 5) The amount of the active compound aetasaifcroa. (1) and the amount of emulsifier were molten together at about 1SO°C and the melt was cooled. The waxy composition was mixed with silica.
S) 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.
B) use Examples Preparations used in the experiments: (a) according to the prior art - tank mix/mixture comparison agent consisting of ®G01iTIX/metBmitron (I), manufactured by Bayer AG, 70 % WG formulation; ®T&AMkT/etho£umas3&te> (XI), manufactured by - IS Schering AG, liquid formulation, active cesmpound content 200 g/1; ®33TAaBHa/phenmedipham (III), manufactured by Schering AG, SC formulation, active compound content 157 g/1. (b) according to the invention the WG finished formulations WG-1 to W6-10 of netamtron a ethofumesate & pheamedipham which are described la the preparation examples.
Experimental set-up; Preparing the active compound preparations: the amounts required of the formulations of the preparations are weighed or measured aad made into spray mixtures using water.
Post-emergence method: test plants are grown in the greenhouse under controlled conditions (standard soil/normal soil, temperature, humidity, light) up to a sire of 5 to 10 ca and then treated with fhe 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: = no actxon/damage (like untreated control) 100 total combating/complete damage Th© f ovulations, application rates, test plants actions can be seea from Tables A-G which follow.
Abbreviations used in the tables: and ACC = active compound 3EA.VA. » Seta vulgaris (beet) AMAHS β Araarantbus retrof issnis GAXiAP = Galium aparizx© MATIM = Matricaria iaodora BSSRAST = Mercuriali® aaaua SOLCO « Bolygonus, convolvulus SIMAL = Sinapis alba Table A-l Post-emergence test/greenhouse (standard soil) Test plants Damage or action in % BEAVA AMARE Formu 1 a t ί on1 ’ Application rate g/ha ACC (a) according to the prior art tank mix/- mixtureι metamitron +e tho £umesafe +phenmedipham 2000+264+272 0 ib) according to· the inventions WG-2 metamitron & ethofumesate & phenmedipham 2000&254&272 0 WG-4 met ami tron & ethofumesate & phenmedipham 2000&264&272 0 100 i CO I WG-7 metamitron 2000&264&272 0 & ethofumesate & phenmedipham ’ in the case of (b), cf in each case the preparation examples (all tables A-F) Test plants Damage or action in % BEAVA AMARE Talkie Post-emergence test/greenhouse (normal soil) Formulation*’ Application ra t© g/ha ACC according to the prior art tank mix/- mixture i met ami tron. -i- e t ho f uflia sate i-phenmedipham 50 0 66 + 68 0 80 according to· the inventions WG-l metamitron & ethofumesate a phenmedipham 500&56&68 0 100 WG-2 metamitron & ethofumesate a phenmedipham 500&S6&63 10 100' Table A-2 (continuation) Post-emergence test/greenhouse (normal soil) Test plants Damage or action. in % BEAVA MARE Formula tion* ’ Application. rate g/ha ACC {b) according to the inventions WG-7 metamitron 500&66&SQ 0 100 & ethofumesate & phenmadipham WG-8 metamitron 500&δδ&δ8 0 90 &. ethofumesate &. phenmedipham i Table Β Post-emergence tesfc/greenhousa (normal soil) Test plants Damage or action in % BEAVA GALAP Po rntu 1 a fc i ona * Application rate g/ha ACC (a) according to the prior art tank mix/mixturei metamitron 1000+132+136 10 80 +ethe fumesate +ph.enmedipham (b) according to the Inventions WG - 3 Eietanitron 1000&132&136 10 90 & ethofuaiesate & phenmedipham Table C Post-emergence test/greenhouse {standard soil) Teat plants Damage or action in % BEAVA MATIN Formulation ‘ ’ Application rate g/ha ACC (a) according to the prior art tank mix/mixtura; metamitron 4000+528+544 20' 90' +ethofumesate +phenmedipham (b) according to , the invention: M WG-1 metamitron & ethofumesabe &. phenmedlpham 100 4000&528&544 I Table D Post-emergence test/greenhouse (standard soil) Test plants Damage or action in % SEAVA MERAN Formulation1’ Application rate g/ha ACC (a) according to the prior art tank mix/mixturst metamitron 4000+528+544 20 90 +· e t ho f uae sate +phenmedipham (b) according to , the inventions - M . ω WG-3 , metamitron 4000&528&544 0 90 & ethofumesate & phenmedipham Table E-l Post-emergence test/greenhouse (standard soil} Formulation*’ Application Test plants rate Damage or action g/ha in % ACC BEAVA POLCO (a) according fo the prior art tank mix/- mixtures metamitron +ethofumesate +phenmedipham 4000+528+544 20 (b) according to the invention: WG-5 metamitron & ethofumesate & phenmedipham 4000&528&544 0 WG-6 metamitron & ethofumesate & phenmedipham 4000&528&544 10 t K5 ifc ’ 100 Table Ξ-2 Post-emergence test/greenhouse (normal soil) Test plants Damage or action in % BEAVA POLCO Formu lation*’ Application rate g/ha ACC (a) according to the prior art tank mix/- mixture: metamitron e tho fume sate +phenmedipham 2000+2S4+272 10 90 (b) according to the inventioni WG-9 metamitron & ethofumesate & phsnxnedipham 2000&264&272 0 100 WG-10 metamitron a ethofumesate & phenxnedipham 2000&264&272 0 100 Table F Post-emergence test/greenhouse (standard soil) Test plants Damage or action in % BEAVA SINAI.
Formula tion*1 Application rate g/ha ACC (a) according to the prior art tank mix/- mixture j metamitron e tho £ use sate +phenmedipham 4000+528+544 20 90 (b) according to the invention? Ϊ WG-5 metamitron & ethofumesate & phenmedipham 4000&528&544 0· 90 w tn 1
Claims (16)
1. Herbicidal agents ia the form of solid finished formulations, containing a combination of the active compounds saefcaiaitron (I) and ethofumesate (XI) and (A.) phenmedipham, (III) or (B) phenmedipham (III) and desmediphaia (IV) ox (C) de smedipham (IV) ,,· in a mixture with formulation auxiliaries, the ratio by weight of the active compounds (I):(II);(III) according to combination (A) being (1):(0.05 to 1):(0.05 to 1), the ratio by weight of the active compounds (I):(II):(III):(IV) according to combination (B) being (1):(0.05 to 1):(0.05 to 1):(0.05 to X) and the ratio by weight of the active compounds (I) : (XI) : (IV) according to combination (C) being (1):(0.05 to 1):(0.05 to 1), and the total active compound content in the combinations (A),, (B) and (C) being between 20 and 75 % by weight.
2. Herbicidal agents according to Claim 1, th© ratio by weight of the active compounds (1):(11):(111) being (1):(0.1 to 0.4):(0.1 to 0.4), oc the active compounds (I):(II):(III):(IV) being (1):(0.1 to 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).
3. Herbicidal agents according fo Claim 1, th© ratio by weight of the active compounds (1):(11):(111) being (1):(0.1 to 0.35):(0.1 to 0.3), of th© active compounds (I)s(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).
4. Herbicidal agents according to Claim 1, the total active compound content In the combinations (A), (3) and (C) being between 30 and 70 %.
5. Solid finished formulations according to Claim 1, carriers, dispersants aad, if appropriate, an emulsifier and/or a wetting agent being employed as formulation auxiliaries. S.
6.Solid finished formulations according to Claim 1 In the form of «rater-dispersible granules.
7. Solid finished formulations according to Claim 1 in tbe form of water-dispersible powders.
8. Solid finished formulations according to Claims 1 and 7 In the form of water-dispersible powders (WP) , 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.
9. Solid finished formulations according to Claims 1 and S In the form of water-dispersible granules (MG), the following formulation auxiliaries additionally being employed per part by weight of met am- itron (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.
10. Process for the preparation of finished formulations in solid fora 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 r indicated in Claim 1, and the mixture is ground and subsequently homogenised by remixing, or in which t the WG (water-dispersible granule) formulations are obtained by (ra) first preparing a premix from the active compounds (I), (II) and (III) or (I), (II), (III) and (IV) or (X), (II) and (IV) - according to the ratios by weight given in Claim 1 -and the formulation auxiliaries which are suitable for a WG formulation by mixing,» grinding, followed by remixing, (b) then treating this premiss 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-S0°C, and (c) separating the 'desired granules (having particle sires between 200 and 1500 pm) by sieving, the too small particles (<200 pa) and the too large particles (>1500 pm) 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. * -30«I I
13. A herbicidal agent according to Claim 1, substantially as hereinbefore described and exemplified.
14. A process for the preparation of a finished formulation according to Claim 1, substantially as hereinbefore 5 described and exemplified.
15. A finished formulation according to Claim 1, whenever prepared by a process claimed in a preceding claim.
16. Use according to Claim 11, substantially as hereinbefore described.
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 |
|---|---|
| IE912359A1 IE912359A1 (en) | 1992-01-15 |
| IE67063B1 true IE67063B1 (en) | 1996-02-21 |
Family
ID=25894790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE235991A IE67063B1 (en) | 1990-07-06 | 1991-07-05 | 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) | FI102029B (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) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5651975A (en) * | 1991-09-27 | 1997-07-29 | Harju-Jeanty; Pontus | Method for the preparation of herbicidal granular products comprising two separate phases |
| FI93416C (en) * | 1991-09-27 | 1995-04-10 | Kemira Oy | Process for the preparation of a herbicide product in granular or tablet form |
| 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 |
| IL104456A (en) * | 1992-01-24 | 1996-12-05 | 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 |
| EP2066172B1 (en) * | 2006-09-14 | 2012-08-15 | Cera Chem S.A.R.L. | Herbicide mixtures with improved activity, stability and pourability for use in beta-beet crops |
| WO2012174105A2 (en) | 2011-06-13 | 2012-12-20 | Lingelbach Fred | Refrigeration system and methods for refrigeration |
| JP6235467B2 (en) | 2011-06-13 | 2017-11-22 | リンゲルバック、フレッド | Condenser / evaporator for cooling device and method thereof |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2413262A1 (en) * | 1974-03-20 | 1975-09-25 | Bayer Ag | Means for selective weed control in turnips |
| YU45662B (en) * | 1983-09-20 | 1992-07-20 | Berol Nobel (Suisse) S.A. | PROCEDURE FOR OBTAINING FENMEDIFAM OR DESMEDIFAM |
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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 AT AT91110322T patent/ATE126418T1/en not_active IP Right Cessation
- 1991-06-22 DK DK91110322.4T patent/DK0465899T3/en active
- 1991-06-22 EP EP91110322A patent/EP0465899B1/en not_active Expired - Lifetime
- 1991-06-22 ES ES91110322T patent/ES2075271T3/en not_active Expired - Lifetime
- 1991-06-22 DE DE59106258T patent/DE59106258D1/en not_active Expired - Lifetime
- 1991-06-27 SK SK1968-91A patent/SK281281B6/en unknown
- 1991-06-27 CZ CS911968A patent/CZ285095B6/en not_active IP Right Cessation
- 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 FI FI913254A patent/FI102029B/en active IP Right Grant
- 1991-07-04 BG BG94756A patent/BG60843B1/en unknown
- 1991-07-04 PL PL91290937A patent/PL167920B1/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 TN TNTNSN91054A patent/TNSN91054A1/en unknown
- 1991-07-05 MA MA22479A patent/MA22206A1/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
- 1991-07-05 YU YU119591A patent/YU48207B/en unknown
- 1991-07-05 SI SI9111195A patent/SI9111195B/en unknown
-
1994
- 1994-08-23 HR HRP-1195/91A patent/HRP940478B1/en not_active IP Right Cessation
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1995
- 1995-08-17 GR GR950402112T patent/GR3017150T3/en unknown
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| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |