CA2168251A1 - Herbicide composition, activity-promoting agent for improving the efficacy of the herbicide, and a method for treating cultivated plants - Google Patents
Herbicide composition, activity-promoting agent for improving the efficacy of the herbicide, and a method for treating cultivated plantsInfo
- Publication number
- CA2168251A1 CA2168251A1 CA002168251A CA2168251A CA2168251A1 CA 2168251 A1 CA2168251 A1 CA 2168251A1 CA 002168251 A CA002168251 A CA 002168251A CA 2168251 A CA2168251 A CA 2168251A CA 2168251 A1 CA2168251 A1 CA 2168251A1
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- Prior art keywords
- activity
- herbicide
- block copolymer
- promoting agent
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A herbicide composition comprising one or more active ingredients, known per se, such as benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea or triazine herbicide, and one or more activity-promoting agents for improving the efficacy of the active ingredient/ingredients. According to the invention, the herbicide comprises at least one activitypromoting agent which is tetraalkoxylated alkyl diamine with general formula (I) in which R1, R2, R3 and R4 are groups which, independent of each other, conform to formula (II), in which one of groups A and B is hydrogen and the other a lower alkyl group, and p+q = 5-150, and n = 1-6, whereby the molecular weight of the compound according to formula (I) is in the range of about 1 000-40 000.
Description
~ t j 21b8~1 W095/03697 PCT ~ 4/00331 HERBICIDE COMPOSITION, A~llVllY-PROMOTING AGENT FOR IMPROVING
THE EFFICACY OF THE HERBICIDE, AND A METHOD FOR TREATING
CULTIVATED PLANTS
This invention relates to a herbicide composition comprising at least one or more active ingredients, known per se, such as bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, or triazine herbicides, and one or more activity-promoting agents for improving the efficacy of the active ingredient/ingredients. The invention further relates to a method for treating plantations such as sugar beet plantations and the like, using a herbicide, and to an activity-promoting agent for increasing the efficacy of the active ingredient of the herbicide, such as benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, or triazine active ingredients.
The efficacy of foliage-applied herbicides can be improved by surface-active additives which decrease the suxface tension of the herbicides, affording more even spreading cf sprayed drops on the surfaces of the leaves thus increasing the area of contact between the herbicide and the leaf surface. Owing to their wax-dissolving properties, lipophilic surface-active additives can also be used to provide more effective penetration of herbicides. Hydrophilic surface-active agents can be used to improve ~he translocation inside plants.
Traditionally, water-insoluble active ingredients have been formulated into emulsion concentrates, and active ingredients insoluble in organic solvents into wettable powders. However, both of these formulations are very user-unfriendly because of - the toxicity and flammability of the solvents, and problems with packaging materials and storage. Wettable powders are problematic because of the heavy dust formation.
Because of the above-described problems, there has been a general attempt to shift to more user-friendly suspensions or granules suspended in water. However, the active ingredients in 2 1 6 ~ 2 5 1 .. . . ,..s,.
WO95/03697 ' PCT/F~4/00331 these are in the form of solid particles, unlike in emulsion concentrates where they are in the form of dissolved molecules, whereby the biological efficacy generally suffers because bigger particles do not penetrate into plants as well as molecules do.
Because of the above, the insoluble active ingredient particles have to be ground into powder of maximum f;n~ness and their penetration and translocation properties improved by activity-promoting agents such as oils, organic solvent additives and/or surface-active agents. Especially, when . using herbicides cont~;n;ng carbamoyl phenyl carbamate, it is necessary to add exceptionally large amounts of these additives in order to achieve sufficient biological efficacy.
Grinding is carried out using air jet mills and suspension mills in order to provide active ingredients of maximum fineness, preferably in the order of 1-5 microns, to ensure the biological effect. Fineness is also required to provide permanent suspensions, improved storage stability of suspension concentrates and improved suspension properties for suspended granules.
English patent publication GB 998264, for instance, shows that ethoxylated fatty amines improve the absorption of certain herbicides, such as paraquat and glyphosate, to the leaves.
However, ethoxylated fatty ~m;nes carry the significant disadvantage of gelling in water, whereby their capability of dissolving the surface waxes of leaves is reduced and the penetration of herbicides is not optimal. On the other hand, increase of the amount of surface-active agents may promote phytotoxic characteristics which damage the host plant. In addition, these ethoxylated fatty amines are extremely hydrophilic, whereby the property brought along by lipophilicity, i.e. enhanced penetration of the herbicide through the wax layer of the leaf, is lacking. Hydrophilic surface-active agents such as fatty ~m; n~s are thus mainly suitable only as additives to hydrophilic active ingredients such as paraquat and glyphosate.
~e ~
2 1 6 ~
~ W095/03697 PCT ~ 4/00331 It is further known~from European patent publication EP 0 257 686 that ethoxy propoxy monoamines can improve the biological efficacy of herbicides. The fatty amines or fatty amido amines/imidazolines formed by this activity-promoting agent contain at least one higher 8-22 C radical connected to one or more nitrogen atoms. The molecular weight of the activity-promoting agent should be less than 2500.
International patent application W0 91/13546 further teaches how to use ethoxy propoxylated block copolymers in the form of water-soluble thermoactive binding agents, as additives for granulation.
EP application publication 417 896 discloses a pesticide composition comprising of a water-insoluble pesticide and a surface active agent. The surface-active agent consists of polyethoxylated poly(ethylene amine) and the ester of polyol and Cl6-C22-unsaturated aliphatic acid.
The purpose of the present invention is to provide an improved herbicide composition.
The purpose of the present invention is especially to provide an improved activity-promoting agent for enhancing the efficacy of the active ingredient of a herbicide. In order to achieve the above objects, the herbicide composition according to the invention is characterized in that the herbicide comprises at least one activity-promoting agent which is tetraalkoxylated alkyl diamine. The e~ficacy of the activity-promoting agent can be advantageously improved in a synergetic way by means of ethoxy propoxy block copolymer. Surprisingly, it has thus been found that tetraalkoxylated alkyl diamines, the general formula - of which is:
~ 35 Rl ~R3 > N - (CH2)n - N ~
R2 R~, in which n = 1-6, 4 - lhe ~ hP~C~k8 , -?~
PCTInte--,~ionalAppllo~kn v 4 216~251 21 -08- l995 A B
Rl, R2, R3 and R4 = - (CH2-CH-O)p - (CH2-~H-O)q - H, p+q = 5-150, and in which one of the compositions A or B is a hydrogen and the other a methyl or an ethyl group, and the molecular weight of which is about 1 000 - 40 000, considerably increase the biological efficacy of the previously mentioned benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, and triazine herbicides on weeds.
The above-mentioned activity-promoting agents are surface-active agents which have been found to have an exceptional property of increasing the biological efficacy of benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, and triazine herbicides generally clearly more so than other surface-active agents used in connection with herbicides usually do. It has been further found that these and some other surface-active agents act synergetically, increasing the biological efficacy of the herbicides in question more than expected of these surface-active agents additively.
The alkoxylated diamines according to the invention have proven to be especially effective in improving the efficacy of herbi-cides on harmful weeds such as lamb's quarters or fathen (Cheno-podium album), bistort (Polygonum spp.), mayweed (Matricaria inodorum), bedstraw (Galium spurium) and rape (Brassica napus).
The molecular weight of the activity-promoting agent according to the invention is preferably 4 000 - 25 000, whereby the size of the molecule does not limit its efficacy, especially on lamb's quarters or fathen.
At the same time, it has been found that ethoxylated propoxy-lated block copolymers, the molecular weights of which are about 2 000 - 20 000, preferably 10 000 - 18 000, act synergetically with tetraalkoxylated alkyl diamines on rape AMEN~
WO95/03697 ~ i 2 1 6 8 2 5 1 PCT/F~4/00331 (Brassica napus), which represents weeds having a considerable layer of wax on the surfaces of their leaves. The hydrophilicity and biological effect of these block copolymers on rape increases with the weight of the molecule. Thus it is probable, on the one hand, that the lipophilicity of the tetraalkoxylated alkyl diamines according to the invention dissolves the surface wax of leaves and increases penetration and, on the other hand, that the hydrophilicity of the ethoxy propoxy block copolymers further increases penetration/translocation.
The activity-promoting agents according to the invention, i.e., tetraalkoxylated diamines and ethoxy propoxylated block copolymers, which both increase the biological efficacy of said active ingredients, can be added into a spray tank as separate activity-promoting tank-mixtures or preferably included in the formulation itself. If the herbicide used is in liquid form, the promoting agents can be mixed with the liquid phase. When using solid herbicides, liquid promoting agents can be absorbed into carriers and those in solid form can be introduced directly into the herbicide mass. The activity-promoting agents can be in the form of separate granules in solid herbicides or they can be incorporated in the same granules with the active ingredients of the herbicides.
The herbicides according to the invention are otherwise formulated in a conventional way. The active ingredients are dissolved in water or organic solvents, suspended in a carrier liquid, or formulated into a solid form. They generally contain about 5-80% of active ingredients. Water, oil, or mixtures of water and oil are generally used as carrier li~uids in suspension concentrates. Surface-active agents (anionic, cationic, non-ionic or ampholytic) are used to provide and improve emulsifiability, dispersibility, suspension stability, wettability, penetration and translocation, and to emulsify the oil in the actual concentrate, and to provide miscibility and suspension/emulsion stability in the final dilution. The preparations can include other additives such as water-miscible and/or water-soluble carriers and/or deflocculation agents such as kaolin or lignin compounds, anti-foam agents (for instance, 2 1 6~25 1 W095/03697 PCT~4/00331 ~
silicone-based agents), thickening agents such as cellulose derivatives, anti-freeze agents in water suspension such as propylene glycol, organic solvents such as kerosine, and colouring agents. In addition, preservatives such as ~ormalin can be used, especially if the preparation contains organic suspending or thickening agents. In the case of wettable granules and pellets, inert inorganic (for instance, silicic acid, salts) or organic (for instance, cellulose, polyacrylates, urea) compounds can be used as carriers to dilute the active ingredients or to adsorb liquid agents.
The active ingredients of herbicide formulations in solid form are advantageously very fine ground, less than lO~m, preferably 1-3~m. Grinding of dry matter is carried out using an air jet mill, for instance, and that of suspensions using a bead mill.
The formulation of suspension concentrates is carried out in a reactor using effective agitation, and the granules or pellets are manufactured by known techniques, for instance, by utilizing disc granulation, spray drying, fluidized bed granulation, mixing granulation using a vertical mixer or a blade mixer, and extrusion, compacting, centrifugal, spraying-bed or spraying/cooling granulations.
The weight ratio of the amounts of activity-promoting agents to the amounts of active ingredients in the formulations is, for instance, from 15:1 to 1:2, preferably from 5:1 to 1:1. An optimal weight ratio of alkoxylated ~; ~ml n~ to ethoxy propoxy block copolymer in a rape-spray is from 1:2 to 1:4. However, in a lamb's quarters or fathen-spray it is more preferable to use a larger amount of alkoxylated ~;~m;ne~ Thus the weight ratio can range in lamb's quarters or fathen-sprays preferably from 10:1 to 1:10.
In addition to the above, other biocides as well as fertilizers can be mixed with the suspension concentrate, granule/pellet, or final dilution. The other biocides include, for instance, other herbicides such as acetamide, diphenyl ether, organophosphorus, pyridine, thiocarbamate, triazine, and uracil herbicides, plant disease control agents, insecticides, and growth regulators. In 1 6 ~ 2 5 ~
W095/03697 PCT/F~4/00331 order to increase the spectrum of control, it is preferable to use for sugar beet and the like, in particular, substances such as lenacil, metolachlor, trichlor acetic acid, EPTC, cycloate, clopyralide, fluroxypyr, benzthiazuron, chlorpropham, fenuron, isocarbimide, propham, trifluralin, alloxydimsodium, sethoxydim, cycloxydim, diallate, fluazifob-butyl, triallate, dalapon, propaquizafop, diclofop-methyl, fenoxaprop-ethyl, quizalofop-ethyl, haloxyfopethoxy ethyl, and proxlmph~m in addition to the above-mentioned agents.
The invention is described in more detail in the following with the aid of examples.
The biological efficacy of herbicides was determined in a greenhouse by means of pot tests. Steady temperature, humidity and lighting conditions were maintained in the greenhouse by automatic means. Generally, the test plants included weeds which cause a lot of harm on sugar beet plantations and the like, such as lamb's quarters or fathen (Chenopodium album = C. album), and rape (Brassica napus = B. napus) whl~- deviate from each other with respect to the surface morpholc of their leaves and thus represent different types of weed. The tests also employed Mercurialis annua (= M. annua) when testing benzofuran herbi-cides, mayweed, i.e., Matricaria inodorum (= M. inodorum), which is sensitive to triazines and pyridazines; black bindweed, i.e., Polygonum r;onvolvulus (= P. convolvulus) was used for testing bipyridines, hydroxybenzonitriles and sulphonyl ureas, and bedstraw, i.e., Galium spurium (= G. spurium) for quinolines and sulphonyl ureas. The susceptibility of cultivated plants to herbicidal injury was determined using seedlings of sugar beet (Beta vulgaris).
The tests generally employed 5-8 seedlings per plant-pot and 3-5 pots in parallel. The amount of water was 200 l/ha, and applicat-- 35 ion was carried out with an automatic dosing sprayer when the weeds were at about the 2-leaf stage. The final estimate on the efficacy of the herbicide was made 13-15 days after the spraying.
In the results below, the efficacy is expressed as the dry or W095/03697 PCT/F~4/00331 ~
fresh weight of the above-ground parts of the weeds or cultivated plants per pot or per seedling.
s The test can be used to show that the alkoxylated diamine (molecular weight MW=6700) according to the invention is clearly more effective than previously known ethoxylated tallow fatty acid amines (E0 15, 20 and 30).
The suspension of active ingredient was prepared from 80%
phenmedipham granules suspended in water. The diamine according to the invention as well as the tallow fatty acid amines were mixed as tank mixture additives to the suspension of active 15ingredient.
Amount of phenmedipham = 720 g/ha Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.1 2.4 2. Alkoxylated diamine 1 0.6 1.6 (MW=6700) 3. Ethoxylated tallow 1 1.2 2.1 fatty acid amine (E0=15) 4. Ethoxylated tallow 1 1.3 2.0 fatty acid amine (EO=20) 5. Ethoxylated tallow 1 1.1 2.4 fatty acid amine (EO=30) 6. Commercial preparation 1 1.3 2.0 Armoblen T/25, ethoxylated tallow fatty acid amine (E0=15) ~ t..'t, ~ t_ ~ WO9S/03697 2 1 6 8 2 5 1 PCT/F~4/00331 Different alkoxylated diamines (MW = 3 600, 6 700, 7 500 and 12 000) were studied by the test. The efficacy was found to improve when the molecular weight was over 3 600, and some kind of optimum was reached when the molecular weight was about 7 000.
Amount of phenmedipham = 720 g/ha Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.7 2.8 2. Alkoxylated diamine 1 1.3 1.9 (MW=3600) 3. Alkoxylated diamine 1 0.8 1.5 (MW=6700) 4. Alkoxylated diamine 1 0.9 1.7 (MM=7500) 5. Alkoxylated diamine 1 1.1 1.7 (MW=12000) The test indicated that both 1 kg/ha alkoxylated diamine (MW=6700) and 1 kg/ha ethoxy prop~y block copolymer (MW=4150) yield a level of efficacy which can not be improved much further on B.napus, even if the dosages are doubled. The alkoxylated diamine (MW=6700) was more effective than the ethoxy propoxy block copolymer (MW=4i-~0), especially on Chenopodium album, and synergy on Brassica napus was observed with a mixture of 20% +
80% (alkoxylated diamine + ethoxy propoxy block copolymer). The mixture of alkoxylated diamine and ethoxy propoxy block copolymer was more effective than a corresponding mixture of ethoxylated tallow fatty acid amine and ethoxy propoxy block copolymer. The alkoxylated diamine (MW=6700) ~s more effective than the ethoxy propoxy block copolymer, especially against 21682~
W095/03697 ~ PCT/F~4/00331 Chenopodium album.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.7 2.8 2. Alkoxylated diamine 0.2 1.5 2.4 3. Alkoxylated diamine 1.0 1.4 2.1 4. Alkoxylated diamine 2.0 0.8 2.1 S. EO-P0 block copolymer 0.2 1.3 2.6 6. E0-P0 block copolymer 1.0 1.4 2.1 7. E0-P0 block copolymer 2.0 1.3 2.0 8. Alkoxylated diamine 0.2 1.4 1.9 E0-P0 block copolymer 0.8 9. Alkoxylated diamine 0.5 1.2 2.1 EO-P0 block copolymer 0.5 10. Alkoxylated diamine 0.8 1.0 2.2 EO-PO block copolymer 0.2 11. Alkoxylated diamine 0.2 1.4 2.1 + E0 tallow fatty acid 0.8 amine 12. E0-P0 monoamine 1 1.7 2.1 The test indicated that the mixture of alkoxylated diamine (MW=
6 700) and ethoxy propoxy copolymer (MW=14 000) was synergetic, especially on Brassica napus. This test also showed that ethoxylated tallow fatty acid amine (E0=15) was less effective than alkoxylated diamines.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
r;.~
~ W095/03697 11 ~1 6 8 ~ 5 I PCT/F~4/00331 Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 1.6 2.2 2. Alkoxylated diamine 1 0.4 1.5 (MW=6700) 3. E0-P0 block copolymer 1 0.6 1.0 (MW=14000) 4. E0-P0 block copolymer 1 0.4 0.9 (MW=14000) 75%
+ alkoxylated diamine (MW=6700) 25%
5. Ethoxylated tallow 1 0.8 1.7 fatty acid amine (E0=15) The test indicated that the molecular weight of ethoxy propoxy block copolymers had no appreciable significance regarding efficacy.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 1.9 2.4 2. E0-P0 block copolymer 1 0.8 1.6 (MW=6600) 3. EO-PO block copolymer 1 0.8 1.4 (MW=12500) 4. EO-P0 block copolymer 1 0.8 1.5 (MW=14000 ) 5. E0-P0 block copolymer 0.7 0.8 1.2 (MW=14000) + alkoxylated diamine 0.2 (MW=6700) + dispersing agent 0.1 W095/03697 ~ ; 12 PCT/~94/00331 The test indicated that the activity-promoting granule according to the invention, consisting of 70~ ethoxy propoxy block copolymer, 20~ alkoxylated ~; ~m; ne and 10~ dispersing agent, enhances the action of ethofumesate and metamitron to a considerable extent. The test also indicated that the activity-promoting granule has a clearly better effect than a conventional oil emulsifier activity-promoting tank-additive, named Actipron (RP) as a commercial preparation, on the weeds studied (Chenopodium album, Matricaria inodorum, Mercurialis annua). However, the active ingredient metamitron has no effect on Mercurialis annua.
Preparation Active ingredient (g/ha) Ethofumesate 70~ WG 400 Metamitron 80~ WG (Goltix/Bayer) 360 Ethofumesate 20~ EC (Kemiron/Kemira) 400 Preparation of the spray as in EXAMPLE 1.
Preparation Activity-prom. Fresh weight (g/seedling) granule kg/ha C.album M.inodorum M.annua 1. Untreated - 1.400 1.176 0.938 2. ~I 0.1 1.263 0.955 0.814 3. " 0.5 1.350 0.938 1.028 4. " 1.0 1.345 0.948 1.033 5. " 2.0 1.323 0.979 1.034 6. Ethofumesate EC - 0.890 1.002 0.485 7. Ethofumesate WG - 1.183 1.039 0.473 8. " 0.1 1.071 0.899 0.475 9. " 0.5 0.783 0.902 0.380 10. " 1.0 0.680 0.960 0.405 11. " 2.0 0.675 0.817 0.384 12. Metamitron - 1.286 0.357 0.917 13. " 0.1 0.898 0.334 0.916 14. Il 0.5 0.468 0.178 0.982 15. " 1.0 0.382 0.256 1.016 16 " 2.0 0.478 0.157 0.962 ~ W095/03697 13 2 1 6 8 2 5 1 PCT/FW/00331 References Actipron ( .ha) 17. Ethofumesate WG 1.0 0.940 0.936 0.415 18. Metamitron WG 1.0 0.865 0.429 1.000 -The test indicates that - there is no appreciable further increase in the enhancing effect of the activity-promoting granule when the amount used exceeds 1 kg/ha, - the emulsifying oil incorporated in the activity-promoting granule improves the efficacy ~urther, especially against Chenopodium album, - the ethoxy propoxy monoamine as a tank mixture additive does not increase the efficacy of the activity-promoting granule on Chenopodium album and that it has an antagonistic, efficacy-reducing effect on Brassica napus.
Amount of phenmedipham = 720 g/ha 80% of the phenmedipham granule and amount of activity-promoting agent = 1 or 2 kg/ha of the activity-promoting granule.
Activity-promoting agent Used amount Dry matter g/pot kg/ha C.album B.napus 1. Untreated - 1.9 2.4 2. E0-P0 block copolymer 0.7 0.8 1.2 + alkoxylated diamine 0.2 + dispersing agent 0.1 3. E0-P0 block copolymer 1.4 0.8 1.0 + alkoxylated diamine 0.4 + dispersing agent 0.2 4. EO-P0 block copolymer 1.2 0.6 0.8 + alkoxylated diamine 0.4 + vegetable oil 0.36 + dispersing agent 0.04 21 632~1 W095/03697 ~ ~ 14 PCT/F~4/00331 5. E0-PO block copolymer 1.4 0.7 1.7 + alkoxylated diamine 0.4 + dispersing agent 0.2 + E0-PO monoamine 1.0 The test investigated the behaviour of a three-part mixture, consisting of phenmedipham (8%) + ethofumesate (10%) +
metamitron (20%), in combination with an activity-promoting agent according to the invention. The results indicate that the mixture of alkoxylated diamine and ethoxy propoxy block copolymer is synergetic. The optimal weight ratio of the mixture, considering both weeds (C. album and B. napus), is about 2:7. The ethoxy propoxy monoamine tested was clearly less effective than the mixture of diamine and ethoxy propoxy block copolymer on both weeds.
The amounts of active ingredients were: phenmedipham 150 g/ha, ethofumesate 190 gJha and metamitron 180 g/ha. The active ingredient granules were suspended in water 200 l/ha and the activity-promoting agents were added in the form of either granules or liquid.
Activity-promoting agent Amount used Dry matter (mg/
kg/ha seedling) C.album B.napus 1. Untreated - 430 390 2. Without prom.agent - 290 380 3. EO-PO block copolymer 0.9 80 240 + dispersing agent 0.1 4. Alkoxylated diamine 0.2 60 170 + E0-P0 block copolymer 0.7 + dispersing agent 0.1 5. Alkoxylated diamine 0.45 40 270 + E0-P0 block copolymer 0.45 + dispersing agent 0.1 6. E0-P0 monoamine 1 170 280 y t S ~ f , C', 1 ~
~ WO9S/03697 2 1 6 ~ 2 5 1 PCT/F~4/00331 A separate ethoxy propoxy monoamine tank mixture additive does not further enhance the action of the granules of a three-part mixture consisting of phenmedipham (8%) + ethofumesate (10%) +
metamitron (20%) and complemented with activity-promoting granules of the optimal mixture of alkoxylated diamine and ethoxy propoxy block copolymer (2:7). Il fact, a clearly antagonistic effect is obtained on Brassica napus.
Amounts of active ingredients:
phenmedipham 150 g/ha ethofumesate 190 g/ha metamitron 380 g/ha The granules of the active ingredients were suspended in water, 200 l/ha, and the ethoxy propoxy monoamine was added in liquid form separately to the spraying dilution at 1 kg/ha.
20Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Untreated - 1.9 2.4 2. Alkoxylated diamine 0.2 0.2 0.8 25+ EO-PO block copolymer 0.7 + dispersing agent 0.1 3. Alkoxylated diamine 0.2 0.2 1.3 + E0-P0 block copolymer 0.7 + dispersing agent 0.1 30+ E0-P0 monoamine 1.0 The test compared a product according to the invention and three products already on the market for efficacy on weeds. At the same time, their effects on host plants were compared. In each case, the active ingredients in the final dilutions were in the form of solid particles of a few microns in size, and the end product was either in solid form granule WG suspendable in ~ F
W095/0307 ~ PCT/F~4/00331 water, or as suspension concentrate SC. The preparation according to the invention contained as activity-promoting agents 10~ alkoxylated ~i~mine + 35~ ethoxy propoxy block copolymer, corresponding to 0.1 kg diamine and 0.35 kg block copolymer per hectare.
The total amount of active ingredients in all the cases was 360 g/ha and the amount of water 200 l/ha.
The test indicated that the preparation according to the invention has a clearly better efficacy than competing products on both frostblite, i.e., Chenopodium album, and rape, i.e., Brassica napus, and that damage to the host plant, which was sugar beet, i.e., Beta w lgaris, is insignificant with all the products studied.
Preparation Active ingredient Dry matter g/pot g/ha C.album B.napus B. w lgaris 1. Untreated - 2.3 2.6 3.0 2. WG according to the invention 360 0.4 1.4 2.9 - phenmedipham 8 - ethofumesate 10 - metamitron 20~
including an activity-promoting agent according to the invention 3. Commercial WG 360 0.9 1.8 2.9 Goltix Triple/Bayer - ph~nmedipham 6.5 - ethofumesate 6.5 - metamitron 28~
4. Commercial SC 360 0.6 1.6 3.2 Betanal Trio SC/Schering - phenmedipham 5 - ethofumesate 5 - metamitron 15~
5. Commercial SC 360 1.2 2.6 2.9 Mentor Star SC/Pluss-Stauffer ~ 31-~
~ O95/03697 17 2 1 6 ~ 2 5 1 PCT/F~4/00331 - phenmedipham 9.2 - ethofumesate 9.2 - metamitron 27.1 ..
The test compared the efficacy of an activity-promoting granule according to the invention with that of a commercial tallow fatty acid amine activity-promoting agent (Armoblen T/25) and a commercial oil-emulsifying activity-promoting agent (Actipron) in different herbicides. Suitable weeds were selected for the herbicides in ~uestion.
The activity-promoting granule according to the invention consisted of 70~ EO-PO block copolymer, 20~ alkoxylated diamine and 10~ dispersing agent.
The studied herbicides by chemical family, their active ingredients, preparation names and dosages we-e as follows:
Chemical family Active ingredient Preparation Dosage of preparation/
ha Bipyridine Diquat dibromide Reglone 0.75 l Hydroxybenzo-nitrile Bromoxynil 80~ WG 0.1875 kg Pyridazine Chloridazon Pyramin FL 3.0 kg Pyridate Lentagran 2.0 kg Quinoline Qll;nmeraC BAS 51802H 2.0 kg Sulphonyl urea Triasulphuron Logran 0.02 kg The test may be used to show that the solid activity-promoting granule according to the invention improves the biological efficacy of the preparations mentioned in the example at least as well as the control li~uid activity-promoting agents Armoblen T/25 and Actipron do when the active ingredient is bromoxynil, chloridazone or triasulphuron. The actions of the other active ingredients are markedly enhanced by the solid activity-improving granule according to the invention as compared with WO95/03697 ~ 18 PCT/F~4/00331 mixtures without activity-promoting agent, and almost as well as by liquid activity-promoting agents.
The spraying mixtures were prepared by mixing the preparations in the above-mentioned amounts with an amount of water corresponding to 200 l/ha, and 1 kg of activity-promoting granule, 1 l of Armoblen T/25 or 1 1 of Actipron per hectare was added as the activity-promoting agent.
Dry matter (mg/seedling) Black bindweed (P.convolvulus) Bipyridine Sulphonyl urea Hydroxy-b e n z o -nitrile (Diquat dibromide)(Triasulphuron)(Bromoxynil) 1. Untreated 726 744 619 2. Without act.
prom.agent143 358 161 3. Activity-promoting granule 43 112 57 4. Actipron 90 182 72 5. Armoblen T/25 31 145 82 Dry matter (mg/seedling) Bedstraw (G.spurium) Mayweed (M.inodorum) Quinoline Sulphonyl urea Pyridazine (Qll;nm~rac)(Triasulphuron) (Chloridazon)(Pyridate) 1. Untreated 194 194 282 282 2. Without prom.
agent 50 94 142 145 3. Activity-prom.
granule 26 20 76 77 4. Actipron 31 22 106 22 5. Armoblen T/25 22 22 109 41
THE EFFICACY OF THE HERBICIDE, AND A METHOD FOR TREATING
CULTIVATED PLANTS
This invention relates to a herbicide composition comprising at least one or more active ingredients, known per se, such as bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, or triazine herbicides, and one or more activity-promoting agents for improving the efficacy of the active ingredient/ingredients. The invention further relates to a method for treating plantations such as sugar beet plantations and the like, using a herbicide, and to an activity-promoting agent for increasing the efficacy of the active ingredient of the herbicide, such as benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, or triazine active ingredients.
The efficacy of foliage-applied herbicides can be improved by surface-active additives which decrease the suxface tension of the herbicides, affording more even spreading cf sprayed drops on the surfaces of the leaves thus increasing the area of contact between the herbicide and the leaf surface. Owing to their wax-dissolving properties, lipophilic surface-active additives can also be used to provide more effective penetration of herbicides. Hydrophilic surface-active agents can be used to improve ~he translocation inside plants.
Traditionally, water-insoluble active ingredients have been formulated into emulsion concentrates, and active ingredients insoluble in organic solvents into wettable powders. However, both of these formulations are very user-unfriendly because of - the toxicity and flammability of the solvents, and problems with packaging materials and storage. Wettable powders are problematic because of the heavy dust formation.
Because of the above-described problems, there has been a general attempt to shift to more user-friendly suspensions or granules suspended in water. However, the active ingredients in 2 1 6 ~ 2 5 1 .. . . ,..s,.
WO95/03697 ' PCT/F~4/00331 these are in the form of solid particles, unlike in emulsion concentrates where they are in the form of dissolved molecules, whereby the biological efficacy generally suffers because bigger particles do not penetrate into plants as well as molecules do.
Because of the above, the insoluble active ingredient particles have to be ground into powder of maximum f;n~ness and their penetration and translocation properties improved by activity-promoting agents such as oils, organic solvent additives and/or surface-active agents. Especially, when . using herbicides cont~;n;ng carbamoyl phenyl carbamate, it is necessary to add exceptionally large amounts of these additives in order to achieve sufficient biological efficacy.
Grinding is carried out using air jet mills and suspension mills in order to provide active ingredients of maximum fineness, preferably in the order of 1-5 microns, to ensure the biological effect. Fineness is also required to provide permanent suspensions, improved storage stability of suspension concentrates and improved suspension properties for suspended granules.
English patent publication GB 998264, for instance, shows that ethoxylated fatty amines improve the absorption of certain herbicides, such as paraquat and glyphosate, to the leaves.
However, ethoxylated fatty ~m;nes carry the significant disadvantage of gelling in water, whereby their capability of dissolving the surface waxes of leaves is reduced and the penetration of herbicides is not optimal. On the other hand, increase of the amount of surface-active agents may promote phytotoxic characteristics which damage the host plant. In addition, these ethoxylated fatty amines are extremely hydrophilic, whereby the property brought along by lipophilicity, i.e. enhanced penetration of the herbicide through the wax layer of the leaf, is lacking. Hydrophilic surface-active agents such as fatty ~m; n~s are thus mainly suitable only as additives to hydrophilic active ingredients such as paraquat and glyphosate.
~e ~
2 1 6 ~
~ W095/03697 PCT ~ 4/00331 It is further known~from European patent publication EP 0 257 686 that ethoxy propoxy monoamines can improve the biological efficacy of herbicides. The fatty amines or fatty amido amines/imidazolines formed by this activity-promoting agent contain at least one higher 8-22 C radical connected to one or more nitrogen atoms. The molecular weight of the activity-promoting agent should be less than 2500.
International patent application W0 91/13546 further teaches how to use ethoxy propoxylated block copolymers in the form of water-soluble thermoactive binding agents, as additives for granulation.
EP application publication 417 896 discloses a pesticide composition comprising of a water-insoluble pesticide and a surface active agent. The surface-active agent consists of polyethoxylated poly(ethylene amine) and the ester of polyol and Cl6-C22-unsaturated aliphatic acid.
The purpose of the present invention is to provide an improved herbicide composition.
The purpose of the present invention is especially to provide an improved activity-promoting agent for enhancing the efficacy of the active ingredient of a herbicide. In order to achieve the above objects, the herbicide composition according to the invention is characterized in that the herbicide comprises at least one activity-promoting agent which is tetraalkoxylated alkyl diamine. The e~ficacy of the activity-promoting agent can be advantageously improved in a synergetic way by means of ethoxy propoxy block copolymer. Surprisingly, it has thus been found that tetraalkoxylated alkyl diamines, the general formula - of which is:
~ 35 Rl ~R3 > N - (CH2)n - N ~
R2 R~, in which n = 1-6, 4 - lhe ~ hP~C~k8 , -?~
PCTInte--,~ionalAppllo~kn v 4 216~251 21 -08- l995 A B
Rl, R2, R3 and R4 = - (CH2-CH-O)p - (CH2-~H-O)q - H, p+q = 5-150, and in which one of the compositions A or B is a hydrogen and the other a methyl or an ethyl group, and the molecular weight of which is about 1 000 - 40 000, considerably increase the biological efficacy of the previously mentioned benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, and triazine herbicides on weeds.
The above-mentioned activity-promoting agents are surface-active agents which have been found to have an exceptional property of increasing the biological efficacy of benzofuran, bipyridine, hydroxybenzonitrile, carbamoyl phenyl carbamate, pyridazine, quinoline, sulphonyl urea, and triazine herbicides generally clearly more so than other surface-active agents used in connection with herbicides usually do. It has been further found that these and some other surface-active agents act synergetically, increasing the biological efficacy of the herbicides in question more than expected of these surface-active agents additively.
The alkoxylated diamines according to the invention have proven to be especially effective in improving the efficacy of herbi-cides on harmful weeds such as lamb's quarters or fathen (Cheno-podium album), bistort (Polygonum spp.), mayweed (Matricaria inodorum), bedstraw (Galium spurium) and rape (Brassica napus).
The molecular weight of the activity-promoting agent according to the invention is preferably 4 000 - 25 000, whereby the size of the molecule does not limit its efficacy, especially on lamb's quarters or fathen.
At the same time, it has been found that ethoxylated propoxy-lated block copolymers, the molecular weights of which are about 2 000 - 20 000, preferably 10 000 - 18 000, act synergetically with tetraalkoxylated alkyl diamines on rape AMEN~
WO95/03697 ~ i 2 1 6 8 2 5 1 PCT/F~4/00331 (Brassica napus), which represents weeds having a considerable layer of wax on the surfaces of their leaves. The hydrophilicity and biological effect of these block copolymers on rape increases with the weight of the molecule. Thus it is probable, on the one hand, that the lipophilicity of the tetraalkoxylated alkyl diamines according to the invention dissolves the surface wax of leaves and increases penetration and, on the other hand, that the hydrophilicity of the ethoxy propoxy block copolymers further increases penetration/translocation.
The activity-promoting agents according to the invention, i.e., tetraalkoxylated diamines and ethoxy propoxylated block copolymers, which both increase the biological efficacy of said active ingredients, can be added into a spray tank as separate activity-promoting tank-mixtures or preferably included in the formulation itself. If the herbicide used is in liquid form, the promoting agents can be mixed with the liquid phase. When using solid herbicides, liquid promoting agents can be absorbed into carriers and those in solid form can be introduced directly into the herbicide mass. The activity-promoting agents can be in the form of separate granules in solid herbicides or they can be incorporated in the same granules with the active ingredients of the herbicides.
The herbicides according to the invention are otherwise formulated in a conventional way. The active ingredients are dissolved in water or organic solvents, suspended in a carrier liquid, or formulated into a solid form. They generally contain about 5-80% of active ingredients. Water, oil, or mixtures of water and oil are generally used as carrier li~uids in suspension concentrates. Surface-active agents (anionic, cationic, non-ionic or ampholytic) are used to provide and improve emulsifiability, dispersibility, suspension stability, wettability, penetration and translocation, and to emulsify the oil in the actual concentrate, and to provide miscibility and suspension/emulsion stability in the final dilution. The preparations can include other additives such as water-miscible and/or water-soluble carriers and/or deflocculation agents such as kaolin or lignin compounds, anti-foam agents (for instance, 2 1 6~25 1 W095/03697 PCT~4/00331 ~
silicone-based agents), thickening agents such as cellulose derivatives, anti-freeze agents in water suspension such as propylene glycol, organic solvents such as kerosine, and colouring agents. In addition, preservatives such as ~ormalin can be used, especially if the preparation contains organic suspending or thickening agents. In the case of wettable granules and pellets, inert inorganic (for instance, silicic acid, salts) or organic (for instance, cellulose, polyacrylates, urea) compounds can be used as carriers to dilute the active ingredients or to adsorb liquid agents.
The active ingredients of herbicide formulations in solid form are advantageously very fine ground, less than lO~m, preferably 1-3~m. Grinding of dry matter is carried out using an air jet mill, for instance, and that of suspensions using a bead mill.
The formulation of suspension concentrates is carried out in a reactor using effective agitation, and the granules or pellets are manufactured by known techniques, for instance, by utilizing disc granulation, spray drying, fluidized bed granulation, mixing granulation using a vertical mixer or a blade mixer, and extrusion, compacting, centrifugal, spraying-bed or spraying/cooling granulations.
The weight ratio of the amounts of activity-promoting agents to the amounts of active ingredients in the formulations is, for instance, from 15:1 to 1:2, preferably from 5:1 to 1:1. An optimal weight ratio of alkoxylated ~; ~ml n~ to ethoxy propoxy block copolymer in a rape-spray is from 1:2 to 1:4. However, in a lamb's quarters or fathen-spray it is more preferable to use a larger amount of alkoxylated ~;~m;ne~ Thus the weight ratio can range in lamb's quarters or fathen-sprays preferably from 10:1 to 1:10.
In addition to the above, other biocides as well as fertilizers can be mixed with the suspension concentrate, granule/pellet, or final dilution. The other biocides include, for instance, other herbicides such as acetamide, diphenyl ether, organophosphorus, pyridine, thiocarbamate, triazine, and uracil herbicides, plant disease control agents, insecticides, and growth regulators. In 1 6 ~ 2 5 ~
W095/03697 PCT/F~4/00331 order to increase the spectrum of control, it is preferable to use for sugar beet and the like, in particular, substances such as lenacil, metolachlor, trichlor acetic acid, EPTC, cycloate, clopyralide, fluroxypyr, benzthiazuron, chlorpropham, fenuron, isocarbimide, propham, trifluralin, alloxydimsodium, sethoxydim, cycloxydim, diallate, fluazifob-butyl, triallate, dalapon, propaquizafop, diclofop-methyl, fenoxaprop-ethyl, quizalofop-ethyl, haloxyfopethoxy ethyl, and proxlmph~m in addition to the above-mentioned agents.
The invention is described in more detail in the following with the aid of examples.
The biological efficacy of herbicides was determined in a greenhouse by means of pot tests. Steady temperature, humidity and lighting conditions were maintained in the greenhouse by automatic means. Generally, the test plants included weeds which cause a lot of harm on sugar beet plantations and the like, such as lamb's quarters or fathen (Chenopodium album = C. album), and rape (Brassica napus = B. napus) whl~- deviate from each other with respect to the surface morpholc of their leaves and thus represent different types of weed. The tests also employed Mercurialis annua (= M. annua) when testing benzofuran herbi-cides, mayweed, i.e., Matricaria inodorum (= M. inodorum), which is sensitive to triazines and pyridazines; black bindweed, i.e., Polygonum r;onvolvulus (= P. convolvulus) was used for testing bipyridines, hydroxybenzonitriles and sulphonyl ureas, and bedstraw, i.e., Galium spurium (= G. spurium) for quinolines and sulphonyl ureas. The susceptibility of cultivated plants to herbicidal injury was determined using seedlings of sugar beet (Beta vulgaris).
The tests generally employed 5-8 seedlings per plant-pot and 3-5 pots in parallel. The amount of water was 200 l/ha, and applicat-- 35 ion was carried out with an automatic dosing sprayer when the weeds were at about the 2-leaf stage. The final estimate on the efficacy of the herbicide was made 13-15 days after the spraying.
In the results below, the efficacy is expressed as the dry or W095/03697 PCT/F~4/00331 ~
fresh weight of the above-ground parts of the weeds or cultivated plants per pot or per seedling.
s The test can be used to show that the alkoxylated diamine (molecular weight MW=6700) according to the invention is clearly more effective than previously known ethoxylated tallow fatty acid amines (E0 15, 20 and 30).
The suspension of active ingredient was prepared from 80%
phenmedipham granules suspended in water. The diamine according to the invention as well as the tallow fatty acid amines were mixed as tank mixture additives to the suspension of active 15ingredient.
Amount of phenmedipham = 720 g/ha Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.1 2.4 2. Alkoxylated diamine 1 0.6 1.6 (MW=6700) 3. Ethoxylated tallow 1 1.2 2.1 fatty acid amine (E0=15) 4. Ethoxylated tallow 1 1.3 2.0 fatty acid amine (EO=20) 5. Ethoxylated tallow 1 1.1 2.4 fatty acid amine (EO=30) 6. Commercial preparation 1 1.3 2.0 Armoblen T/25, ethoxylated tallow fatty acid amine (E0=15) ~ t..'t, ~ t_ ~ WO9S/03697 2 1 6 8 2 5 1 PCT/F~4/00331 Different alkoxylated diamines (MW = 3 600, 6 700, 7 500 and 12 000) were studied by the test. The efficacy was found to improve when the molecular weight was over 3 600, and some kind of optimum was reached when the molecular weight was about 7 000.
Amount of phenmedipham = 720 g/ha Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.7 2.8 2. Alkoxylated diamine 1 1.3 1.9 (MW=3600) 3. Alkoxylated diamine 1 0.8 1.5 (MW=6700) 4. Alkoxylated diamine 1 0.9 1.7 (MM=7500) 5. Alkoxylated diamine 1 1.1 1.7 (MW=12000) The test indicated that both 1 kg/ha alkoxylated diamine (MW=6700) and 1 kg/ha ethoxy prop~y block copolymer (MW=4150) yield a level of efficacy which can not be improved much further on B.napus, even if the dosages are doubled. The alkoxylated diamine (MW=6700) was more effective than the ethoxy propoxy block copolymer (MW=4i-~0), especially on Chenopodium album, and synergy on Brassica napus was observed with a mixture of 20% +
80% (alkoxylated diamine + ethoxy propoxy block copolymer). The mixture of alkoxylated diamine and ethoxy propoxy block copolymer was more effective than a corresponding mixture of ethoxylated tallow fatty acid amine and ethoxy propoxy block copolymer. The alkoxylated diamine (MW=6700) ~s more effective than the ethoxy propoxy block copolymer, especially against 21682~
W095/03697 ~ PCT/F~4/00331 Chenopodium album.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 2.7 2.8 2. Alkoxylated diamine 0.2 1.5 2.4 3. Alkoxylated diamine 1.0 1.4 2.1 4. Alkoxylated diamine 2.0 0.8 2.1 S. EO-P0 block copolymer 0.2 1.3 2.6 6. E0-P0 block copolymer 1.0 1.4 2.1 7. E0-P0 block copolymer 2.0 1.3 2.0 8. Alkoxylated diamine 0.2 1.4 1.9 E0-P0 block copolymer 0.8 9. Alkoxylated diamine 0.5 1.2 2.1 EO-P0 block copolymer 0.5 10. Alkoxylated diamine 0.8 1.0 2.2 EO-PO block copolymer 0.2 11. Alkoxylated diamine 0.2 1.4 2.1 + E0 tallow fatty acid 0.8 amine 12. E0-P0 monoamine 1 1.7 2.1 The test indicated that the mixture of alkoxylated diamine (MW=
6 700) and ethoxy propoxy copolymer (MW=14 000) was synergetic, especially on Brassica napus. This test also showed that ethoxylated tallow fatty acid amine (E0=15) was less effective than alkoxylated diamines.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
r;.~
~ W095/03697 11 ~1 6 8 ~ 5 I PCT/F~4/00331 Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 1.6 2.2 2. Alkoxylated diamine 1 0.4 1.5 (MW=6700) 3. E0-P0 block copolymer 1 0.6 1.0 (MW=14000) 4. E0-P0 block copolymer 1 0.4 0.9 (MW=14000) 75%
+ alkoxylated diamine (MW=6700) 25%
5. Ethoxylated tallow 1 0.8 1.7 fatty acid amine (E0=15) The test indicated that the molecular weight of ethoxy propoxy block copolymers had no appreciable significance regarding efficacy.
Amount of phenmedipham = 720 g/ha.
Preparation of the spray as in EXAMPLE 1.
Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Without prom.agent - 1.9 2.4 2. E0-P0 block copolymer 1 0.8 1.6 (MW=6600) 3. EO-PO block copolymer 1 0.8 1.4 (MW=12500) 4. EO-P0 block copolymer 1 0.8 1.5 (MW=14000 ) 5. E0-P0 block copolymer 0.7 0.8 1.2 (MW=14000) + alkoxylated diamine 0.2 (MW=6700) + dispersing agent 0.1 W095/03697 ~ ; 12 PCT/~94/00331 The test indicated that the activity-promoting granule according to the invention, consisting of 70~ ethoxy propoxy block copolymer, 20~ alkoxylated ~; ~m; ne and 10~ dispersing agent, enhances the action of ethofumesate and metamitron to a considerable extent. The test also indicated that the activity-promoting granule has a clearly better effect than a conventional oil emulsifier activity-promoting tank-additive, named Actipron (RP) as a commercial preparation, on the weeds studied (Chenopodium album, Matricaria inodorum, Mercurialis annua). However, the active ingredient metamitron has no effect on Mercurialis annua.
Preparation Active ingredient (g/ha) Ethofumesate 70~ WG 400 Metamitron 80~ WG (Goltix/Bayer) 360 Ethofumesate 20~ EC (Kemiron/Kemira) 400 Preparation of the spray as in EXAMPLE 1.
Preparation Activity-prom. Fresh weight (g/seedling) granule kg/ha C.album M.inodorum M.annua 1. Untreated - 1.400 1.176 0.938 2. ~I 0.1 1.263 0.955 0.814 3. " 0.5 1.350 0.938 1.028 4. " 1.0 1.345 0.948 1.033 5. " 2.0 1.323 0.979 1.034 6. Ethofumesate EC - 0.890 1.002 0.485 7. Ethofumesate WG - 1.183 1.039 0.473 8. " 0.1 1.071 0.899 0.475 9. " 0.5 0.783 0.902 0.380 10. " 1.0 0.680 0.960 0.405 11. " 2.0 0.675 0.817 0.384 12. Metamitron - 1.286 0.357 0.917 13. " 0.1 0.898 0.334 0.916 14. Il 0.5 0.468 0.178 0.982 15. " 1.0 0.382 0.256 1.016 16 " 2.0 0.478 0.157 0.962 ~ W095/03697 13 2 1 6 8 2 5 1 PCT/FW/00331 References Actipron ( .ha) 17. Ethofumesate WG 1.0 0.940 0.936 0.415 18. Metamitron WG 1.0 0.865 0.429 1.000 -The test indicates that - there is no appreciable further increase in the enhancing effect of the activity-promoting granule when the amount used exceeds 1 kg/ha, - the emulsifying oil incorporated in the activity-promoting granule improves the efficacy ~urther, especially against Chenopodium album, - the ethoxy propoxy monoamine as a tank mixture additive does not increase the efficacy of the activity-promoting granule on Chenopodium album and that it has an antagonistic, efficacy-reducing effect on Brassica napus.
Amount of phenmedipham = 720 g/ha 80% of the phenmedipham granule and amount of activity-promoting agent = 1 or 2 kg/ha of the activity-promoting granule.
Activity-promoting agent Used amount Dry matter g/pot kg/ha C.album B.napus 1. Untreated - 1.9 2.4 2. E0-P0 block copolymer 0.7 0.8 1.2 + alkoxylated diamine 0.2 + dispersing agent 0.1 3. E0-P0 block copolymer 1.4 0.8 1.0 + alkoxylated diamine 0.4 + dispersing agent 0.2 4. EO-P0 block copolymer 1.2 0.6 0.8 + alkoxylated diamine 0.4 + vegetable oil 0.36 + dispersing agent 0.04 21 632~1 W095/03697 ~ ~ 14 PCT/F~4/00331 5. E0-PO block copolymer 1.4 0.7 1.7 + alkoxylated diamine 0.4 + dispersing agent 0.2 + E0-PO monoamine 1.0 The test investigated the behaviour of a three-part mixture, consisting of phenmedipham (8%) + ethofumesate (10%) +
metamitron (20%), in combination with an activity-promoting agent according to the invention. The results indicate that the mixture of alkoxylated diamine and ethoxy propoxy block copolymer is synergetic. The optimal weight ratio of the mixture, considering both weeds (C. album and B. napus), is about 2:7. The ethoxy propoxy monoamine tested was clearly less effective than the mixture of diamine and ethoxy propoxy block copolymer on both weeds.
The amounts of active ingredients were: phenmedipham 150 g/ha, ethofumesate 190 gJha and metamitron 180 g/ha. The active ingredient granules were suspended in water 200 l/ha and the activity-promoting agents were added in the form of either granules or liquid.
Activity-promoting agent Amount used Dry matter (mg/
kg/ha seedling) C.album B.napus 1. Untreated - 430 390 2. Without prom.agent - 290 380 3. EO-PO block copolymer 0.9 80 240 + dispersing agent 0.1 4. Alkoxylated diamine 0.2 60 170 + E0-P0 block copolymer 0.7 + dispersing agent 0.1 5. Alkoxylated diamine 0.45 40 270 + E0-P0 block copolymer 0.45 + dispersing agent 0.1 6. E0-P0 monoamine 1 170 280 y t S ~ f , C', 1 ~
~ WO9S/03697 2 1 6 ~ 2 5 1 PCT/F~4/00331 A separate ethoxy propoxy monoamine tank mixture additive does not further enhance the action of the granules of a three-part mixture consisting of phenmedipham (8%) + ethofumesate (10%) +
metamitron (20%) and complemented with activity-promoting granules of the optimal mixture of alkoxylated diamine and ethoxy propoxy block copolymer (2:7). Il fact, a clearly antagonistic effect is obtained on Brassica napus.
Amounts of active ingredients:
phenmedipham 150 g/ha ethofumesate 190 g/ha metamitron 380 g/ha The granules of the active ingredients were suspended in water, 200 l/ha, and the ethoxy propoxy monoamine was added in liquid form separately to the spraying dilution at 1 kg/ha.
20Activity-promoting agent Amount used Dry matter g/pot kg/ha C.album B.napus 1. Untreated - 1.9 2.4 2. Alkoxylated diamine 0.2 0.2 0.8 25+ EO-PO block copolymer 0.7 + dispersing agent 0.1 3. Alkoxylated diamine 0.2 0.2 1.3 + E0-P0 block copolymer 0.7 + dispersing agent 0.1 30+ E0-P0 monoamine 1.0 The test compared a product according to the invention and three products already on the market for efficacy on weeds. At the same time, their effects on host plants were compared. In each case, the active ingredients in the final dilutions were in the form of solid particles of a few microns in size, and the end product was either in solid form granule WG suspendable in ~ F
W095/0307 ~ PCT/F~4/00331 water, or as suspension concentrate SC. The preparation according to the invention contained as activity-promoting agents 10~ alkoxylated ~i~mine + 35~ ethoxy propoxy block copolymer, corresponding to 0.1 kg diamine and 0.35 kg block copolymer per hectare.
The total amount of active ingredients in all the cases was 360 g/ha and the amount of water 200 l/ha.
The test indicated that the preparation according to the invention has a clearly better efficacy than competing products on both frostblite, i.e., Chenopodium album, and rape, i.e., Brassica napus, and that damage to the host plant, which was sugar beet, i.e., Beta w lgaris, is insignificant with all the products studied.
Preparation Active ingredient Dry matter g/pot g/ha C.album B.napus B. w lgaris 1. Untreated - 2.3 2.6 3.0 2. WG according to the invention 360 0.4 1.4 2.9 - phenmedipham 8 - ethofumesate 10 - metamitron 20~
including an activity-promoting agent according to the invention 3. Commercial WG 360 0.9 1.8 2.9 Goltix Triple/Bayer - ph~nmedipham 6.5 - ethofumesate 6.5 - metamitron 28~
4. Commercial SC 360 0.6 1.6 3.2 Betanal Trio SC/Schering - phenmedipham 5 - ethofumesate 5 - metamitron 15~
5. Commercial SC 360 1.2 2.6 2.9 Mentor Star SC/Pluss-Stauffer ~ 31-~
~ O95/03697 17 2 1 6 ~ 2 5 1 PCT/F~4/00331 - phenmedipham 9.2 - ethofumesate 9.2 - metamitron 27.1 ..
The test compared the efficacy of an activity-promoting granule according to the invention with that of a commercial tallow fatty acid amine activity-promoting agent (Armoblen T/25) and a commercial oil-emulsifying activity-promoting agent (Actipron) in different herbicides. Suitable weeds were selected for the herbicides in ~uestion.
The activity-promoting granule according to the invention consisted of 70~ EO-PO block copolymer, 20~ alkoxylated diamine and 10~ dispersing agent.
The studied herbicides by chemical family, their active ingredients, preparation names and dosages we-e as follows:
Chemical family Active ingredient Preparation Dosage of preparation/
ha Bipyridine Diquat dibromide Reglone 0.75 l Hydroxybenzo-nitrile Bromoxynil 80~ WG 0.1875 kg Pyridazine Chloridazon Pyramin FL 3.0 kg Pyridate Lentagran 2.0 kg Quinoline Qll;nmeraC BAS 51802H 2.0 kg Sulphonyl urea Triasulphuron Logran 0.02 kg The test may be used to show that the solid activity-promoting granule according to the invention improves the biological efficacy of the preparations mentioned in the example at least as well as the control li~uid activity-promoting agents Armoblen T/25 and Actipron do when the active ingredient is bromoxynil, chloridazone or triasulphuron. The actions of the other active ingredients are markedly enhanced by the solid activity-improving granule according to the invention as compared with WO95/03697 ~ 18 PCT/F~4/00331 mixtures without activity-promoting agent, and almost as well as by liquid activity-promoting agents.
The spraying mixtures were prepared by mixing the preparations in the above-mentioned amounts with an amount of water corresponding to 200 l/ha, and 1 kg of activity-promoting granule, 1 l of Armoblen T/25 or 1 1 of Actipron per hectare was added as the activity-promoting agent.
Dry matter (mg/seedling) Black bindweed (P.convolvulus) Bipyridine Sulphonyl urea Hydroxy-b e n z o -nitrile (Diquat dibromide)(Triasulphuron)(Bromoxynil) 1. Untreated 726 744 619 2. Without act.
prom.agent143 358 161 3. Activity-promoting granule 43 112 57 4. Actipron 90 182 72 5. Armoblen T/25 31 145 82 Dry matter (mg/seedling) Bedstraw (G.spurium) Mayweed (M.inodorum) Quinoline Sulphonyl urea Pyridazine (Qll;nm~rac)(Triasulphuron) (Chloridazon)(Pyridate) 1. Untreated 194 194 282 282 2. Without prom.
agent 50 94 142 145 3. Activity-prom.
granule 26 20 76 77 4. Actipron 31 22 106 22 5. Armoblen T/25 22 22 109 41
Claims (12)
1. A herbicide composition comprising at least - one or more active ingredients, known per se, which is a benzofuran, a bipyridine, a hydroxybenzonitrile, a carbamoyl phenyl carbamate, a pyridazine, a quinoline, a sulphonyl urea, or a triazine herbicide, and - one or more activity-promoting agents for improving the efficacy of the active ingredient/ingredients, c h a r a c t e r i z e d in that the activity-promoting agent is a tetraalkoxylated alkyl diamine with the following general formula (I):
- (CH2)n - (I) in which R1, R2, R3 and R4 are groups which, independent of each other, conform to the following formula:
, in which one of groups A and B is a hydrogen and the other a lower alkyl group, and p+q = 5-150, and n = 1-6, whereby the molecular weight of the compound according to formula (I) is in the range of about 1 000-40 000.
- (CH2)n - (I) in which R1, R2, R3 and R4 are groups which, independent of each other, conform to the following formula:
, in which one of groups A and B is a hydrogen and the other a lower alkyl group, and p+q = 5-150, and n = 1-6, whereby the molecular weight of the compound according to formula (I) is in the range of about 1 000-40 000.
2. A herbicide composition according to Claim 1, c h a r a c t e r i z e d in that the active ingredient is methyl-3-m-tolyl-carbamoyl oxyphenyl carbamate and/or ethyl-3-phenyl carbamoyl oxyphenyl carbamate and/or 2-ethoxy-2,3-dihydro-3,3-dimethyl benzofuran-5-ylmethane sulphonate and/or 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5-(4H)-one, and/or 1,1'-ethylene-2,2'-dipyridyliumdibromide, and/or 3,5-dibromo-4-hydroxy benzonitrile and/or 5-amino-4-chlorine-2-phenylpyrid-azine-3-(2H)-one, and/or 6-chloro-3-phenylpyridazine-4-yl-S-octyl tiocarbonate, and/or 7-chloro-3-methyl-8-quinoline carboxylic acid, and/or 3-(6-methoxy-4-methyl-1,3,5-triazine-2-yl)-1-[2-(2-chlorethoxy)phenyl sulphonyl] urea.
3. A herbicide composition according to Claim 1 or 2, c h a r a c t e r i z e d in that it further comprises ethoxy propoxy block copolymer as a synergetic additive.
4. A herbicide composition according to Claim 3, c h a r a c t e r i z e d in that the ethoxy propoxy block copolymer conforms to the following general formula (II):
HO-[(CH2-CH2-O)r - (CHa -CH2-O)s)]t - H (II) in which r and s are mainly > 5 and t has such a value that the molecular weight of the ethoxy propoxy copolymer is in the range of 2 000 - 20 000.
HO-[(CH2-CH2-O)r - (CHa -CH2-O)s)]t - H (II) in which r and s are mainly > 5 and t has such a value that the molecular weight of the ethoxy propoxy copolymer is in the range of 2 000 - 20 000.
5. A herbicide composition according to Claim 4, c h a r a c t e r i z e d in that the ratio of the amount of ethoxy propoxy block copolymer to the amount of the tetraalkoxylated alkyl diamine is preferably 1:10 - 10:1 by weight.
6. A herbicide composition according to Claim 1, c h a r a c t e r i z e d in that the ratio of the amount of the activity-promoting agent to the amount of the active ingredient is preferably 1:5 - 10:1 by weight.
7. A herbicide composition according to Claim 1, c h a r a c t e r i z e d in that it further contains other substances such as carriers and encapsulating agents as well as additives intended for emulsification, dispersing, suspending, antifreezing, stabilizing and/or antifoaming, and/or other activity-promoting agents.
8. A herbicide composition according to Claim 2, c h a r a c t e r i z e d in that it simultaneously further comprises other pesticides such as acetamide, diphenyl ether, organophosphorus, pyridine, thiocarbamate, triazine, and uracil herbicides.
9. A method for destroying weeds, c h a r a c t e r i z e d in that weeds are treated with a herbicide composition according to any of the preceding Claims.
10. An activity-promoting agent for improving the efficacy of the active ingredient of a herbicide, which active agent is a benzofuran, a bipyridine, a hydroxybenzonitrile, a carbamoyl phenyl carbamate, a pyridazine, a quinoline, a sulphonyl urea or triazine active compound, c h a r a c t e r i z e d in that the activity-promoting agent comprises tetraalkoxylated alkyl diamine, the general formula (I) of which is:
- ( CH2 )n - (I) in which R1, R2, R3 and R4 are groups which, independent of each other, conform to the formula:
-(CH2 - O)p - (CH2 - O)q - H, in which one of groups A and B is a hydrogen and the other a lower alkyl group, and p + q = 5 - 150, and n = 1 - 6, whereby the molecular weight of the composition according to formula (I) is in the range of about 1 000 - 40 000.
- ( CH2 )n - (I) in which R1, R2, R3 and R4 are groups which, independent of each other, conform to the formula:
-(CH2 - O)p - (CH2 - O)q - H, in which one of groups A and B is a hydrogen and the other a lower alkyl group, and p + q = 5 - 150, and n = 1 - 6, whereby the molecular weight of the composition according to formula (I) is in the range of about 1 000 - 40 000.
11. An activity-promoting agent according to Claim 10, c h a r a c t e r i z e d in that the activity-promoting agent comprises ethoxy propoxy block copolymer as a synergetic additive in addition to the tetraalkoxylated alkyl diamine.
12. An activity-promoting agent according to Claim 11, c h a r a c t e r i z e d in that the ethoxy propoxy block copolymer conforms to the following general formula (II):
HO-[(CH2-CH2-O)r - (CH2-CH2-O)s)]t - H (II) in which r and s are mainly > 5 and t has such a value that the molecular weight of the ethoxy propoxy copolymer is in the range of 2 000 - 20 000.
HO-[(CH2-CH2-O)r - (CH2-CH2-O)s)]t - H (II) in which r and s are mainly > 5 and t has such a value that the molecular weight of the ethoxy propoxy copolymer is in the range of 2 000 - 20 000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI933374A FI933374A (en) | 1993-07-28 | 1993-07-28 | Herbicidal composition, enhancer for improving the effectiveness of herbicide and method for treating crops |
| FI933374 | 1993-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2168251A1 true CA2168251A1 (en) | 1995-02-09 |
Family
ID=8538359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002168251A Abandoned CA2168251A1 (en) | 1993-07-28 | 1994-07-27 | Herbicide composition, activity-promoting agent for improving the efficacy of the herbicide, and a method for treating cultivated plants |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0711112A1 (en) |
| JP (1) | JPH09500892A (en) |
| BG (1) | BG100317A (en) |
| CA (1) | CA2168251A1 (en) |
| CZ (1) | CZ25696A3 (en) |
| EE (1) | EE9400099A (en) |
| FI (1) | FI933374A (en) |
| LT (1) | LT96006A (en) |
| NO (1) | NO960346L (en) |
| PL (1) | PL312780A1 (en) |
| SI (1) | SI9400304A (en) |
| SK (1) | SK12596A3 (en) |
| WO (1) | WO1995003697A1 (en) |
| YU (1) | YU48094A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629260A (en) * | 1995-07-26 | 1997-05-13 | Basf Corporation | Heteric EO/PO block copolymers as adjuvants for herbicidal formulations |
| AUPO405696A0 (en) | 1996-12-06 | 1997-01-09 | Ici Australia Operations Proprietary Limited | Herbicidal compositions |
| GB0625591D0 (en) * | 2006-12-21 | 2007-01-31 | Agrovista Uk Ltd | Herbicide composition |
| EP2090166A1 (en) * | 2008-02-14 | 2009-08-19 | Bayer CropScience AG | Liquid herbicidal preparations |
| TWI827660B (en) * | 2018-09-13 | 2024-01-01 | 日商住友化學股份有限公司 | Bipyridine compound and use thereof |
| CN109169680A (en) * | 2018-09-14 | 2019-01-11 | 江苏好收成韦恩农化股份有限公司 | Herbicidal composition and preparation method thereof for Sugarbeet Fields |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289581A (en) * | 1978-04-05 | 1981-09-15 | Katayama Chemical Works Co., Ltd. | Microbicidal slimicide compositions for industrial use |
| DE3767946D1 (en) * | 1986-08-20 | 1991-03-14 | Akzo Nv | HERBICIDES AND FUNGICIDES CONTAINING EFFECTIVE ADDITIVES. |
| US4954338A (en) * | 1987-08-05 | 1990-09-04 | Rohm And Haas Company | Microbicidal microemulsion |
| FR2648316A1 (en) * | 1989-06-20 | 1990-12-21 | Rhone Poulenc Agrochimie | HERBICIDE COMPOSITIONS BASED ON N-PHOSPHONOMETHYLGLYCIN AND THEIR USE |
| JPH0774124B2 (en) * | 1989-07-26 | 1995-08-09 | 竹本油脂株式会社 | Method for preparing water-based pesticide formulation composition and water-based pesticide formulation composition obtained by the method |
-
1993
- 1993-07-28 FI FI933374A patent/FI933374A/en not_active Application Discontinuation
-
1994
- 1994-07-27 CA CA002168251A patent/CA2168251A1/en not_active Abandoned
- 1994-07-27 EP EP94921670A patent/EP0711112A1/en not_active Ceased
- 1994-07-27 WO PCT/FI1994/000331 patent/WO1995003697A1/en not_active Application Discontinuation
- 1994-07-27 JP JP7505601A patent/JPH09500892A/en active Pending
- 1994-07-27 CZ CZ96256A patent/CZ25696A3/en unknown
- 1994-07-27 SK SK125-96A patent/SK12596A3/en unknown
- 1994-07-27 YU YU48094A patent/YU48094A/en unknown
- 1994-07-27 PL PL94312780A patent/PL312780A1/en unknown
- 1994-07-28 SI SI9400304A patent/SI9400304A/en unknown
- 1994-09-16 EE EE9400099A patent/EE9400099A/en unknown
-
1996
- 1996-01-26 NO NO960346A patent/NO960346L/en unknown
- 1996-01-26 LT LT96-006A patent/LT96006A/en unknown
- 1996-01-29 BG BG100317A patent/BG100317A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CZ25696A3 (en) | 1996-06-12 |
| FI933374A0 (en) | 1993-07-28 |
| NO960346L (en) | 1996-03-26 |
| FI933374A (en) | 1995-01-29 |
| LT96006A (en) | 1996-05-27 |
| YU48094A (en) | 1997-08-22 |
| WO1995003697A1 (en) | 1995-02-09 |
| PL312780A1 (en) | 1996-05-13 |
| SI9400304A (en) | 1995-04-30 |
| EP0711112A1 (en) | 1996-05-15 |
| JPH09500892A (en) | 1997-01-28 |
| NO960346D0 (en) | 1996-01-26 |
| EE9400099A (en) | 1995-12-15 |
| BG100317A (en) | 1997-03-31 |
| SK12596A3 (en) | 1997-02-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |