EP0497806A1 - Selective herbicides - Google Patents

Selective herbicides

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Publication number
EP0497806A1
EP0497806A1 EP19900915442 EP90915442A EP0497806A1 EP 0497806 A1 EP0497806 A1 EP 0497806A1 EP 19900915442 EP19900915442 EP 19900915442 EP 90915442 A EP90915442 A EP 90915442A EP 0497806 A1 EP0497806 A1 EP 0497806A1
Authority
EP
European Patent Office
Prior art keywords
contain
composition according
weight
component
esters
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.)
Withdrawn
Application number
EP19900915442
Other languages
German (de)
French (fr)
Inventor
Rudolf Heinrich
Thomas Maier
Hans Schumacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Hoechst AG
Hoechst Schering Agrevo GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG, Hoechst Schering Agrevo GmbH filed Critical Hoechst AG
Publication of EP0497806A1 publication Critical patent/EP0497806A1/en
Withdrawn legal-status Critical Current

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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N25/02—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 containing liquids as carriers, diluents or solvents
    • 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
    • A01N25/22—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 containing ingredients stabilising the active ingredients
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles

Definitions

  • the invention relates to new liquid selective herbicidal compositions which contain active compounds from the group of phenoxy herbicides and the optionally substituted l-aryl-3-alkoxycarbonyl-5-alkyl-l, 2,4-triazoles in the form of chemically and application-technically stable emulsion concentrates.
  • Formulation auxiliaries and stabilizers can have a negative influence on one another at elevated storage temperatures and then, particularly with longer storage times, undergo noticeable chemical changes and lead to less biologically effective or even ineffective components. These disadvantages are overcome with the present invention.
  • the present invention relates to liquid selective herbicidal compositions based on emulsion concentrates, characterized in that they
  • e contain one or more emulsifiers and, if appropriate, wetting agents and customary additives.
  • herbicidal phenoxy or heteroaryloxyphenoxycarboxylic acid esters for example, the known optionally substituted phenoxyphenoxy, quinoxalyloxyphenoxy, pyridyloxyphenoxy, Benzoxazolyloxyphenoxy- or Benzthiazolyloxyphenoxy- carboxylic acid esters, in the form of the pure optical isomers or as mixtures of isomers (eg racemates).
  • the compounds are described, for example, in DE-A 2,136,828 (US-A 4,238,626); DE-A 2,223,894
  • Suitable herbicides of component a) are, for example, the active compounds
  • the active substances mentioned are preferred in the D, L or in particular the enriched or pure D form.
  • herbicidal active ingredient diclofop-methyl or fenoxaprop-ethyl are particularly preferred.
  • the above-mentioned active ingredients are also largely described in "The Pesticide Manual", 8th ed. 1987, British Crop Protection Council.
  • Suitable compounds for component b) of the agents according to the invention are the compounds mentioned in EP-A-0174562, preferably the 1- (2,4-
  • Dichlorophenyl -) - 3- (C ⁇ -C ⁇ alkoxyJcarbonyl-S-haloalkyl-1,2,4-triazole compounds, especially the 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-haloalkyl-1 , 2,4-triazoles, the haloalkyl radical preferably being CCI3, CHC1 2 , CHF 2 CF 2 .
  • esters from carboxylic acids or phosphoric acid with alcohols, diols or polyols are of particular interest, for example esters from aliphatic C2-C5 carboxylic acids or phosphoric acid and linear or branched aliphatic C ⁇ -C - ⁇ - alcohols. Diols or polyols.
  • Esters of carboxylic acids such as acetic acid, propionic acid, butanoic acid or pentanoic acid, in particular acetic acid, or of orthophosphoric acid with alcohols, such as methanol, ethanol, propanol, isopropanol, n-, i-, t- and 2-butanol, n-, i- or 2-pentanol, n-, i- or 2-hexanol, heptanol, octanol, nonanol, decanol, undecanol and dodecanol, or diols, such as glycol, propanediol, butanediol and hexanediol, or polyols, such as glycerol, pentaerythritol and hexitol .
  • alcohols such as methanol, ethanol, propanol, isopropanol, n-, i-,
  • phosphoric acid esters such as tri-n-butyl phosphate or esters of acetic acid with C2-Cg alcohols or with diols such as 1,4-butanediol or with triols such as glycerol, in particular the esters butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, nonylacetate, l 4-bis (acetoxy) butane and glycerol triacetate.
  • Suitable as component d) are, for example, organic solvents such as aliphatic or aromatic
  • Hydrocarbons aliphatic cyclic and acyclic ketones, N-methylpyrrolidone, dimethylformamide, alkylene glycol mono- and diesters or corresponding ethers, in particular solvents with a high proportion of aromatics.
  • Suitable aromatic solvents are toluene, xylenes, higher-boiling aromatic fractions and methylnaphthalenes, and cyclohexanehexn is particularly suitable as a ketone.
  • Suitable components e) are conventional emulsifiers, preferably one or more from the group comprising alkylbenzenesulfonates, such as calcium dodecylsulfonate, and fatty acid polyglycol esters, such as ethoxylated castor oil. Any wetting agents contained are preferably from the group of alkylphenol polyglycol ethers and alkanol polyglycol ethers.
  • EO ethyleneoxy units
  • the products ⁇ Emulsogen EL 400 or ⁇ __mulsogen EL 360 (from Hoechst AG) can be used.
  • the fatty acid polyglycol esters contain in particular 12-18 carbon atoms in the fatty acid part.
  • the ethoxylated alkylphenols are especially nonylphenols and preferably contain 20-200 EO. These include, for example, ⁇ Arkopal N 100 (Hoechst AG).
  • Preferred alkanol polyglycol ethers are ethoxylated (Cg-C2 Q ) alkanols with an EO content of 3 to 20 EO, for example ®Genapol X 060 (Hoechst AG).
  • emulsifiers and wetting agents ethoxylated castor oil and the alkanol polyglycol ethers are particularly suitable according to the invention.
  • the herbicidal compositions according to the invention can contain further conventional additives for emulsion concentrates, for example stabilizers against moisture, such as, for example, acid anhydrides, substituted amines and epoxy compounds such as epoxidized linseed oil or soybean oil.
  • stabilizers against moisture such as, for example, acid anhydrides, substituted amines and epoxy compounds such as epoxidized linseed oil or soybean oil.
  • the herbicidal compositions according to the invention generally contain 5-50% by weight, preferably 20-35% by weight of components a) and b), 2-20% by weight, in particular 5-15% by weight of component c ), further 5-40 wt .-%, preferably 10-25 wt .-% solvent and 10-30 wt .-%, preferably 15-25 wt .-% emulsifiers and wetting agents.
  • the ratio of the active ingredient components a) and b) to one another in the formulations is preferably from 5: 1 to 1: 3.
  • the optimal amount of component c) depends on the amount of active ingredients a) and b) and can easily be determined in preliminary tests.
  • the invention further relates to a method for producing the agents according to the invention.
  • the above-mentioned components are mixed in the required amounts at temperatures of preferably 10 ° to 60 ° C., expediently at room temperature or slightly above, until a homogeneous solution of the individual components has formed.
  • the solvent or solvent mixture is first placed in a kettle with a stirrer; then the two active ingredient components a) and b) are added and the mixture is stirred until a clear solution is obtained.
  • the compounds of component c) to be used according to the invention are slowly allowed to flow into these and then the emulsifiers and, if appropriate, wetting agents and other additives are added. Then the mixture is stirred until a clear solution is obtained.
  • the entire process is conveniently carried out at room temperature or slightly above. The order of adding the components can also be different.
  • the emulsion concentrate prepared which corresponds to a practically water-free solution of components a), b), c) and e) in the organic solvent, is extremely stable against chemical degradation of the active ingredients and against phase separations, such as, for example, the precipitation of components, even in comparison high drug content. They are therefore very stable in storage and suitable for storage under climatically unfavorable conditions, especially at high temperatures of 30 to 50 ° C. Before the emulsion concentrates are used biologically, they are mixed with water and give emulsions which are perfect in terms of use and whose effectiveness is not inferior to the combinations of the active substances a) and b) which may have been formulated in the spray tank.
  • Example 2 The experiment from Example 1 is repeated, instead of of 10 wt .-% glycerol triacetate, the same amount of xylene is added. The sample is also stored for 3 months at 50 ° C and then analyzed analytically.
  • Example 2 The experiment from Example 2 is repeated, the same being used instead of the 10% by weight of tri-n-butyl phosphoric acid Amount of xylene is added. The sample is also stored for 3 months at 50 ° C and then analyzed analytically.
  • Fatty acid polyglycol ester (with 36 EO) and stir until clear solution.
  • 5% by weight of epoxidized linseed oil, 5% by weight of dodecylbenzenesulfonic acid calcium and 12% by weight of hexyl acetate are added to the mixture, and stirring is continued for about 20 minutes.
  • Example 3 The experiment from Example 3 is repeated, with the same amount of xylene being added instead of the 12% by weight of hexyl acetate.
  • the sample is also stored for 3 months at 50 ° C and then analyzed analytically. Salary, salary according to baseline 3 months / 50 ° C
  • Triazole compound 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl- 5- (1,1,2,2-tetrafluoroethyl) -1,2,4-triazole.
  • the emulsion concentrate obtained is stable over 3 months at 50 ° C. and in particular shows no significant degradation in the active substance content.
  • the emulsion concentrates obtained according to the preparation examples are mixed with water on the

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Les herbicides selon l'invention sont des formulations stables à base de concentrats en émulsion renfermant: a) un ou plusieurs esters d'acides phénoxyphénoxy ou hétéroaryloxy-phénoxy-carboxyliques, b) un ou plusieurs composés appartenant au groupe des 1-aryl-3-alkoxycarbonyl-5-alkyl-1,2,4-triazols éventuellement substitués, c) un ou plusieurs esters d'acide carboxylique ou d'acide phosphorique avec des monoalcools, des dialcools ou des polyalcools aliphatiques, en tant qu'agents stabilisants, d) un ou plusieurs solvants organiques avec, notamment une fraction prépondérante en solvants aromatiques, et, e) un ou plusieurs émulsifiants et, le cas échéant, des agents mouillants et des adjuvants de types courants.The herbicides according to the invention are stable formulations based on emulsion concentrates containing: a) one or more esters of phenoxyphenoxy or heteroaryloxy-phenoxy-carboxylic acids, b) one or more compounds belonging to the group of 1-aryl-3 -alkoxycarbonyl-5-alkyl-1,2,4-triazols optionally substituted, c) one or more esters of carboxylic acid or phosphoric acid with monoalcohols, dialcohols or aliphatic polyalcohols, as stabilizing agents, d) one or more organic solvents with, in particular a predominant fraction of aromatic solvents, and, e) one or more emulsifiers and, where appropriate, wetting agents and adjuvants of common types.

Description

Selektive herbizide MittelSelective herbicidal agents
Die Erfindung betrifft neue flüssige selektive herbizide Mittel, die Wirkstoffe aus der Gruppe der Phenoxy-Herbizide und der gegebenenfalls substituierten l-Aryl-3- alkoxycarbonyl-5-alkyl-l,2,4-triazole in Form chemisch und anwendungstechnisch stabiler Emulsionskonzentrate enthalten.The invention relates to new liquid selective herbicidal compositions which contain active compounds from the group of phenoxy herbicides and the optionally substituted l-aryl-3-alkoxycarbonyl-5-alkyl-l, 2,4-triazoles in the form of chemically and application-technically stable emulsion concentrates.
Es ist bekannt, Verbindungen aus der Gruppe der Phenoxy- phenoxy-Herbizide und der Benzoxazolyloxy-phenoxy-Herbizide mit anderen selektiv herbizid wirkenden Verbindungen oder mit Kulturpfl nzen schützenden Mitteln (Safenern) zum Zwecke einer Optimierung des WirkungsSpektrums zu chemisch und anwendungstechnisch stabilen Fertigformulierungen zu kombinieren.It is known to combine compounds from the group of the phenoxyphenoxy herbicides and the benzoxazolyloxyphenoxy herbicides with other selectively herbicidally active compounds or with crop protection agents (safeners) for the purpose of optimizing the spectrum of action to give chemically and application-technically stable finished formulations .
Aus EP-A-0174562 (US-A-4,639,266) ist unter anderem bekannt, Benzoxazolyloxy-phenoxy-Herbizide, wie z.B. 2- (4- (6-Chlor-2-benzoxazolyloxy)-phenox -propionsäureethylester (Fenoxapropethyl) mit Safenern aus der Gruppe der gegebenenfalls substituierten l-Aryl-3-alkoxycarbonyl-5- alkyl-l,2,4-triazol-Verbindungen in der Weise zu kombinieren, daß der Spritzbrühe kurz vor der Applikation des Fenoxapropethyl entsprechende Anteile einer Formulierung des genannten 1,2,4-Triazolε zugesetzt werden, um auf diese Weise die vorteilhaften biologischenFrom EP-A-0174562 (US-A-4,639,266) it is known, inter alia, benzoxazolyloxyphenoxy herbicides, such as e.g. Ethyl 2- (4- (6-chloro-2-benzoxazolyloxy) phenoxypropionate (fenoxapropethyl) with safeners from the group of optionally substituted 1-aryl-3-alkoxycarbonyl-5-alkyl-1,2,4-triazole compounds to combine in such a way that appropriate proportions of a formulation of the 1,2,4-triazole mentioned are added to the spray mixture shortly before the application of the fenoxapropethyl, in order in this way to obtain the advantageous biological
Eigenschaften der Kombination beider Wirkstoffe zu nutzen. Dieses Verfahren ist jedoch umständlich und zeitraubend und kann in der Praxis leicht zu Fehldosierungen führen.To use properties of the combination of both active ingredients. However, this procedure is cumbersome and time-consuming and can easily lead to incorrect dosing in practice.
Es bestand daher die Aufgabe, diese Schwierigkeiten zu umgehen und biologisch wirksame, homogene und chemisch sowie anwendungstechnisch stabile Zubereitungen dieser beiden Wirkstoffe herzustellen, die den in der Praxis gestellten Anforderungen entsprechen. Dabei war insbesondere zu beachten, daß sich die beiαen Wirkstoffklassen in Gegenwart üblicherThe task was therefore to circumvent these difficulties and to produce biologically active, homogeneous and chemically and application-technically stable preparations of these two active ingredients which meet the requirements set in practice. It was particularly important to note that the two classes of active substances are more common in the presence
Formulierungshilfsmittel und Stabilisatoren bei erhöhten Lagertemperaturen gegenseitig negativ beeinflussen können und sich dann, vor allem bei längeren Lagerzeiten, chemisch merklich verändern und zu biologisch weniger wirksamen oder gar unwirksamen Komponenten führen. Diese Nachteile werden mit der vorliegenden Erfindung überwunden.Formulation auxiliaries and stabilizers can have a negative influence on one another at elevated storage temperatures and then, particularly with longer storage times, undergo noticeable chemical changes and lead to less biologically effective or even ineffective components. These disadvantages are overcome with the present invention.
Gegenstand der vorliegenden Erfindung sind flüssige selektiv herbizide Mittel auf Basis von Emulsionskonzentraten, dadurch gekennzeichnet, daß sieThe present invention relates to liquid selective herbicidal compositions based on emulsion concentrates, characterized in that they
a) einen oder mehrere herbizide Phenoxyphenoxy- oder Heteroaryloxy-phenoxy-carbonsäureester,a) one or more herbicidal phenoxyphenoxy or heteroaryloxyphenoxy-carboxylic acid esters,
b) ein oder mehrere Verbindungen aus der Gruppe der gegebenenfalls substituierten l-Aryl-3-alkoxycarbonyl- 5-alkyl-l,2,4-triazole,b) one or more compounds from the group of optionally substituted l-aryl-3-alkoxycarbonyl-5-alkyl-l, 2,4-triazoles,
c) ein oder mehrere Carbonsäure- oder Phosphorsäureester von aliphatischen Mono-,Di- oder Polyalkoholen als stabilisierendes Agens,c) one or more carboxylic acid or phosphoric acid esters of aliphatic mono-, di- or polyalcohols as a stabilizing agent,
d) ein oder mehrere organische Lösungsmittel, insbesondere mit einem überwiegenden Teil an aromatischen Lösungsmitteln, undd) one or more organic solvents, in particular with a predominant proportion of aromatic solvents, and
e) ein oder mehrere Emulgatoren und gegebenenfalls Netzmittel und übliche Zusatzstoffe enthalten.e) contain one or more emulsifiers and, if appropriate, wetting agents and customary additives.
Als herbizide Phenoxy- oder Heteroaryloxy- phenoxycarbonsäureester (Komponente a) können beispielsweise die bekannten gegebenenfalls substituierten Phenoxyphenoxy- , Chinoxalyloxyphenoxy- , Pyridyloxyphenoxy-, Benzoxazolyloxyphenoxy- oder Benzthiazolyloxyphenoxy- carbonsäureester, in Form der reinen optischen Isomeren oder als Isomerengemische (z.B. Racemate) eingesetzt werden. Die Verbindungen sind beispielsweise in DE-A 2,136,828 (US-A 4,238,626); DE-A 2,223,894As herbicidal phenoxy or heteroaryloxyphenoxycarboxylic acid esters (component a), for example, the known optionally substituted phenoxyphenoxy, quinoxalyloxyphenoxy, pyridyloxyphenoxy, Benzoxazolyloxyphenoxy- or Benzthiazolyloxyphenoxy- carboxylic acid esters, in the form of the pure optical isomers or as mixtures of isomers (eg racemates). The compounds are described, for example, in DE-A 2,136,828 (US-A 4,238,626); DE-A 2,223,894
(US-A 3,954,442); GB-PS 2,0432,539; GB-PS 1,599,121; DE-A 2,640,730 (US-A 4,130,413) beschrieben. In Frage kommen insbesondere die (C-L-C4)Alkyl-, (C2~C4)Alkenyl- oder (C3-C4)Alkinyl-ester.(US-A 3,954,442); GB-PS 2,0432,539; GB-PS 1,599,121; DE-A 2,640,730 (US-A 4,130,413). In particular, the (CLC 4 ) alkyl, (C2 ~ C4) alkenyl or (C 3 -C 4 ) alkynyl esters come into question.
Geeignete Herbizide der Komponente a) sind beispielsweise die WirkstoffeSuitable herbicides of component a) are, for example, the active compounds
2- (4- (2,4-Dichlorphenoxy)-phenoxy)-propionsäuremethylester (Diclofop- ethyl),2- (4- (2,4-dichlorophenoxy) phenoxy) propionic acid methyl ester (diclofopethyl),
2- (4- (4-Brom-2-chlorphenoxy)-phenoxy)- propionsäure ethylester,2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionic acid ethyl ester,
2- (4- (4-Trifluormethylphenoxy)-phenoxy)- propionsäuremethylester,Methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate,
2- (4- (2-Chlor-4-trifluormethylphenoxy)-phenoxy)- propionsäureme'thylester,2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) - propionsäureme 'acid methyl ester,
4- (4- (4-Trifluormethylphenoxy)-phenoxy)-pent-2-en- säureethylester,4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-enoic acid ethyl ester,
2- (4- (3,5-Dichlorpyridyl-2-oxy)-phenoxy)- propionsäureethylester,Ethyl 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionate,
2- (4- (3-Chlor-5-trifluormethyl-pyridyl-2-oxy)- phenoxypropionsäure-methylester- oder -2-ethoxyethylester (Haloxyfop-methyl oder Haloxyfop-2-ethoxy-ethyl),2- (4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) - phenoxypropionic acid methyl ester or -2-ethoxyethyl ester (haloxyfop-methyl or haloxyfop-2-ethoxy-ethyl),
2- (4- (3,5-Dichlorpyridyl-2-oxy)-phenoxy)- propionsäurepropargylester, 2- (4- (6-Chlorbenzoxazol-2-yl-cxy)-phenoxy)- propionsäureethylester (Fenoxaprop-ethyl) ,2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid propargyl ester, 2- (4- (6-chlorobenzoxazol-2-yl-cxy) phenoxy) propionic acid ethyl ester (fenoxaprop-ethyl),
2- (4- (6-Chlorbenzthiazol-2-yl-oxy)-phenoxy)- propionsäureethylester (Fenthiaprop-ethyl),Ethyl 2- (4- (6-chlorobenzthiazol-2-yl-oxy) phenoxy) propionate (fenthiaprop-ethyl),
2- (4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)-phenoxy)-. propionsäuremethylester,2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) -. methyl propionate,
2- (4- (5-Trifluormethyl-2-pyridyloxy-)-phenox_)- propionsäurebutylester (Fluazifop-butyl),2- (4- (5-trifluoromethyl-2-pyridyloxy -) - phenox _) - butyl propionate (fluazifop-butyl),
2- (4- ( 6-Chlor-2- chinoxalyloxy)-phenox2jt propionsäureethylester ( uiz alofop- ethyl ) ,Ethyl 2- (4- (6-chloro-2-quinoxalyloxy) -phenoxyl propionate (uiz alofop-ethyl),
2- (4- ( 6-Fluor-2- chinoxalyloxy)-phenoxy)- propionsäureethylester.2- (4- (6-Fluoro-2-quinoxalyloxy) phenoxy) propionic acid ethyl ester.
Bevorzugt sind die genannten Wirkstoffe in der D,L- oder insbesondere der angereicherten oder reinen D-Form.The active substances mentioned are preferred in the D, L or in particular the enriched or pure D form.
Besonders bevorzugt sind erfindungsgemäße Mittel mit dem herbiziden Wirkstoff Diclofop-methyl oder Fenoxaprop-ethyl. Die obengenannten Wirkstoffe sind zum großen Teil auch in "The Pesticide Manual", 8. Aufl. 1987, British Crop Protection Council beschrieben.Agents according to the invention with the herbicidal active ingredient diclofop-methyl or fenoxaprop-ethyl are particularly preferred. The above-mentioned active ingredients are also largely described in "The Pesticide Manual", 8th ed. 1987, British Crop Protection Council.
Geeignete Verbindungen für die Komponente b) der erfindungsgemäßen Mittel sind die in der EP-A-0174562 genannten Verbindungen, vorzugsweise die l-(2,4-Suitable compounds for component b) of the agents according to the invention are the compounds mentioned in EP-A-0174562, preferably the 1- (2,4-
Dichlorphenyl-)-3- (C^-C^-alkoxyJcarbonyl-S-halogenalkyl- 1,2,4-triazol-Verbindungen, insbesondere die l-(2,4- Dichlorphenyl)-3-ethoxycarbonyl-5-halogenalkyl-1,2,4- triazole, wobei der Halogenalkylrest vorzugsweise CCI3, CHC12, CHF2CF2 bedeutet. Als Komponente c) mit stabilisierender Wirkung sind niedrigmolekulare Ester aus Carbonsäuren oder Phosphorsäure mit Alkoholen, Diolen oder Polyolen von besonderem Interesse, beispielsweise Ester aus aliphatischen C2-C5-Carbonsäuren oder Phosphorsäure und linearen oder verzweigten aliphatischen C^-C-^-Alkoholen, -Diolen oder -Polyolen. Bevorzugt sind dabei Ester von Carbonsäuren, wie Essigsäure, Propionsäure, Butansäure oder Pentansäure, insbesondere Essigsäure, oder von Orthophosphorsäure mit Alkoholen, wie Methanol, Ethanol, Propanol, Isopropanol, n- , i- , t- und 2-Butanol, n-, i- oder 2-Pentanol, n-, i- oder 2-Hexanol, Heptanol, Octanol, Nonanol, Decanol, Undecanol und Dodecanol, oder Diolen, wie Glykol, Propandiol, Butandiol und Hexandiol, oder Polyolen, wie Glycerin, Pentaerythrit und Hexit.Dichlorophenyl -) - 3- (C ^ -C ^ alkoxyJcarbonyl-S-haloalkyl-1,2,4-triazole compounds, especially the 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-haloalkyl-1 , 2,4-triazoles, the haloalkyl radical preferably being CCI3, CHC1 2 , CHF 2 CF 2 . As component c) with a stabilizing effect, low molecular weight esters from carboxylic acids or phosphoric acid with alcohols, diols or polyols are of particular interest, for example esters from aliphatic C2-C5 carboxylic acids or phosphoric acid and linear or branched aliphatic C ^ -C - ^ - alcohols. Diols or polyols. Esters of carboxylic acids, such as acetic acid, propionic acid, butanoic acid or pentanoic acid, in particular acetic acid, or of orthophosphoric acid with alcohols, such as methanol, ethanol, propanol, isopropanol, n-, i-, t- and 2-butanol, n-, i- or 2-pentanol, n-, i- or 2-hexanol, heptanol, octanol, nonanol, decanol, undecanol and dodecanol, or diols, such as glycol, propanediol, butanediol and hexanediol, or polyols, such as glycerol, pentaerythritol and hexitol .
Bevorzugt sind insbesondere Phosphorsäureester wie Tri-n- butylphosphat oder Ester von Essigsäure mit C2-Cg-Alkoholen oder mit Diolen wie 1,4-Butandiol oder mit Triolen wie Glycerin, insbesondere die Ester Butylacetat, Pentylacetat, Hexylacetat, Heptylacetat, Nonylacetat, l,4-Bis(acetoxy)- butan und Glycerintriacetat.Particularly preferred are phosphoric acid esters such as tri-n-butyl phosphate or esters of acetic acid with C2-Cg alcohols or with diols such as 1,4-butanediol or with triols such as glycerol, in particular the esters butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, nonylacetate, l 4-bis (acetoxy) butane and glycerol triacetate.
Als Komponente d) eignen sich beispielsweise organische Lösungsmittel wie aliphatische oder aromatischeSuitable as component d) are, for example, organic solvents such as aliphatic or aromatic
Kohlenwasserstoffe, aliphatische cyclische und acyclische Ketone, N-Methylpyrrolidon, Dimethylformamid, Alkylenglykolmono- und -diester oder entsprechende Ether, insbesondere Lösungsmittel mit einem hohen Anteil an Aromaten.Hydrocarbons, aliphatic cyclic and acyclic ketones, N-methylpyrrolidone, dimethylformamide, alkylene glycol mono- and diesters or corresponding ethers, in particular solvents with a high proportion of aromatics.
Als aromatische Lösungsmittel eignen sich beispielsweise Toluol, Xylole, höher siedende Aromatenfraktionen und Methylnaphthaline, und als Keton eignet sich insbesondere Cyclohexanόn. Als Komponente e) eignen sich übliche Emulgatoren, vorzugsweise ein oder mehrere aus der Gruppe, enthaltend Alkylbenzolsulfonate, wie dodecylsulfonεaures Calcium, und Fettsäurepolyglykolester, wie ethoxyliertes Rizinusöl. Gegebenenfalls enthaltene Netzmittel sind vorzugsweise aus der Gruppe der Alkylphenolpolyglykolether und Alkanolpolyglykolether.Examples of suitable aromatic solvents are toluene, xylenes, higher-boiling aromatic fractions and methylnaphthalenes, and cyclohexanehexn is particularly suitable as a ketone. Suitable components e) are conventional emulsifiers, preferably one or more from the group comprising alkylbenzenesulfonates, such as calcium dodecylsulfonate, and fatty acid polyglycol esters, such as ethoxylated castor oil. Any wetting agents contained are preferably from the group of alkylphenol polyglycol ethers and alkanol polyglycol ethers.
Das erfindungsgemäß einsetzbare ethoxylierte Rizinusöl oder ethoxylierte Rizinussäure enthält insbesondere 20 bis 60 EO (EO = Ethylenoxyeinheiten) . Beispielsweise können die Produkte ©Emulsogen EL 400 oder β__mulsogen EL 360 (Fa. Hoechst AG) eingesetzt werden. Die Fettsäurepolyglykolester enthalten insbesondere 12-18 C-Atome im Fettsäureteil. Die ethoxylierten Alkylphenole sind insbesondere Nonylphenole und enthalten vorzugsweise 20-200 EO. Zu diesen zählt beispielsweise ©Arkopal N 100 (Fa. Hoechst AG). Als Alkanolpolyglykolether sind bevorzugt ethoxylierte (Cg-C2Q)Alkanole mit einem EO-Gehalt von 3 bis 20 EO, z.B. ®Genapol X 060 (Fa. Hoechst AG) zu nennen. Von den genannten Emulgatoren und Netzmitteln eignen sich erfindungsgemäß besonders ethoxyliertes Rizinusöl und die Alkanolpolyglykolether.The ethoxylated castor oil or ethoxylated castor acid which can be used according to the invention contains in particular 20 to 60 EO (EO = ethyleneoxy units). For example, the products © Emulsogen EL 400 or β __mulsogen EL 360 (from Hoechst AG) can be used. The fatty acid polyglycol esters contain in particular 12-18 carbon atoms in the fatty acid part. The ethoxylated alkylphenols are especially nonylphenols and preferably contain 20-200 EO. These include, for example, © Arkopal N 100 (Hoechst AG). Preferred alkanol polyglycol ethers are ethoxylated (Cg-C2 Q ) alkanols with an EO content of 3 to 20 EO, for example ®Genapol X 060 (Hoechst AG). Of the emulsifiers and wetting agents mentioned, ethoxylated castor oil and the alkanol polyglycol ethers are particularly suitable according to the invention.
Die erfindungsgemäßen herbiziden Mittel können weitere übliche Zusatzstoffe für Emulsionskonzentrate enthalten, beispielsweise Stabilisatoren gegen Feuchtigkeit, wie beispielsweise Säureanhydride, substituierte Amine und EpoxyVerbindungen wie epoxidiertes Leinöl oder Sojaöl.The herbicidal compositions according to the invention can contain further conventional additives for emulsion concentrates, for example stabilizers against moisture, such as, for example, acid anhydrides, substituted amines and epoxy compounds such as epoxidized linseed oil or soybean oil.
Die erfindungsgemäßen herbiziden Mittel enthalten in der Regel 5-50 Gew.-%, bevorzugt 20-35 Gew.-% der Komponennten a) und b), 2-20 Gew.-%, insbesondere 5-15 Gew.-% Komponente c), ferner 5-40 Gew.-%, bevorzugt 10-25 Gew.-% Lösungsmittel sowie 10-30 Gew.-%, bevorzugt 15-25 Gew.-% Emulgatoren und Netzmittel. Das Verhältnis der Wirkstoff omponenten a) und b) zueinander ist in den Formulierungen bevorzugt von 5:1 bis 1:3. Die optimale Menge an Komponente c) hängt von der Menge an Wirkstoffen a) und b) ab und kann in Vorversuchen leicht ermittelt werden.The herbicidal compositions according to the invention generally contain 5-50% by weight, preferably 20-35% by weight of components a) and b), 2-20% by weight, in particular 5-15% by weight of component c ), further 5-40 wt .-%, preferably 10-25 wt .-% solvent and 10-30 wt .-%, preferably 15-25 wt .-% emulsifiers and wetting agents. The ratio of the active ingredient components a) and b) to one another in the formulations is preferably from 5: 1 to 1: 3. The optimal amount of component c) depends on the amount of active ingredients a) and b) and can easily be determined in preliminary tests.
Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung der erfindungsgemäßen Mittel. Hierzu werden die obengenannten Komponenten in den erforderlichen Mengen bei Temperaturen von vorzugsweise 10° bis 60°C, zweckmäßigerweise bei Raumtemperatur oder leicht darüber, gemischt bis sich eine homogene Lösung der einzelnen Komponenten gebildet hat.The invention further relates to a method for producing the agents according to the invention. For this purpose, the above-mentioned components are mixed in the required amounts at temperatures of preferably 10 ° to 60 ° C., expediently at room temperature or slightly above, until a homogeneous solution of the individual components has formed.
Zur praktischen Durchführung des Verfahrens wird zunächst das Lösungsmittel oder Lösungsmittelgemisch in einem Kessel mit Rührer vorgelegt; anschließend gibt man die beiden Wirkstoff omponenten a) und b) zu und rührt bis zu klaren Lösung. In diese läßt man langsam die erfindungsgemäß einzusetzenden Verbindungen der Komponente c) zufließen und setzt dann die Emulgatoren und gegebenenf lls Netzmittel und weitere Zusatzstoffe zu. Danach läßt man rühren, bis eine klare Lösung entsteht. Der gesamte Vorgang wird zweckmäßigerweise bei Raumtemperatur oder leicht darüber durchgeführt. Die Reihenfolge der Zugabe der Komponenten kann auch anders sein.To carry out the process in practice, the solvent or solvent mixture is first placed in a kettle with a stirrer; then the two active ingredient components a) and b) are added and the mixture is stirred until a clear solution is obtained. The compounds of component c) to be used according to the invention are slowly allowed to flow into these and then the emulsifiers and, if appropriate, wetting agents and other additives are added. Then the mixture is stirred until a clear solution is obtained. The entire process is conveniently carried out at room temperature or slightly above. The order of adding the components can also be different.
Das hergestellte Emulsionεkonzentrat, das einer praktisch wasserfreien Lösung der Komponenten a) , b), c) und e) in dem organischen Lösungsmittel entspricht, ist hervorragend stabil gegen chemischen Abbau der Wirkstoffe und gegen Phasentrennungen, wie z.B. das Ausfallen von Komponenten, auch bei vergleichsweise hohen Wirkstoffgehalten. Sie sind deshalb sehr gut lagerstabil und für die Lagerung unter klimatisch ungünstigen Bedingungen, insbesondere auch bei hohen Temperaturen von 30 bis 50°C, geeignet. Vor der biologischen Anwendung der Emulsionskonzentrate werden diese mit Wasser gemischt und ergeben anwendungstechnische einwandfreie Emulsionen, die in ihrer Wirksamkeit den im Spritztank hergestellten Kombinationen der gegebenenfalls formulierten Wirkstoffe a) und b) nicht nachstehen.The emulsion concentrate prepared, which corresponds to a practically water-free solution of components a), b), c) and e) in the organic solvent, is extremely stable against chemical degradation of the active ingredients and against phase separations, such as, for example, the precipitation of components, even in comparison high drug content. They are therefore very stable in storage and suitable for storage under climatically unfavorable conditions, especially at high temperatures of 30 to 50 ° C. Before the emulsion concentrates are used biologically, they are mixed with water and give emulsions which are perfect in terms of use and whose effectiveness is not inferior to the combinations of the active substances a) and b) which may have been formulated in the spray tank.
Die olgenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to illustrate the invention:
Beispiel 1example 1
9,5 Gew.-% Fenoxaprop-P-ethyl (I) (D-isomer von Fenoxaprop¬ ethyl) werden in 42 Gew.-% Xylol unter Rühren bei 25-30°C gelöst. Zu der klaren Lösung setzt man 4,7 Gew.-%9.5% by weight of Fenoxaprop-P-ethyl (I) (D-isomer of Fenoxaprop¬ ethyl) are dissolved in 42% by weight of xylene with stirring at 25-30 ° C. 4.7% by weight is added to the clear solution
1- (2,4-Dichlorphenyl)-3-ethoxycarbonyl-5-trichlormethyl- 1,2,4-triazol (II) und danach 12 Gew.-% eines C^-C-j^- Fettalkoholpolyglykoläthers (mit 6 EO) und 6,8 Gew.-% eines c12"c18~Fettsäurepolyglykolesters (mit 40 E0) zu und rührt bis zur klaren Lösung.1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-trichloromethyl-1,2,4-triazole (II) and then 12% by weight of a C ^ -C- j ^ - fatty alcohol polyglycol ether (with 6 EO) and 6.8% by weight of a c 12 " c 18 ~ fatty acid polyglycol ester ( with 40 E0 ) and stirred until a clear solution.
Zu dieser gibt man 5,0 Gew.-% epoxidiertes Sojaöl, 10,0 Gew.-% einer xylolischen Lösung des Ca-Salzes der Dodecyl- benzolsulfonsäure und 10 Gew.-% Glycerin-triacetat und läßt 20 Minuten nachrühren.To this are added 5.0% by weight of epoxidized soybean oil, 10.0% by weight of a xylene solution of the Ca salt of dodecylbenzenesulfonic acid and 10% by weight of glycerol triacetate and the mixture is stirred for 20 minutes.
Ein Teil der Probe wird 3 Monate bei 50°C gelagert und danach analytisch untersucht:Part of the sample is stored for 3 months at 50 ° C and then analyzed analytically:
Gehalt, Gehalt nachSalary, salary after
Ausgangswert 3 Mon./50°CInitial value 3 months / 50 ° C
Verbindung I 9,2 Gew.-% 9,1 Gew.-%Compound I 9.2% by weight 9.1% by weight
Verbindung II 4,6 " 4,6 "Compound II 4.6 "4.6"
Vergleichsbeispiel 1Comparative Example 1
Der Versuch aus Beispiel 1 wird wiederholt, wobei anstelle von 10 Gew.-% Glycerin-triacetat die gleiche Menge Xylol zugesetzt wird. Die Probe wird ebenfalls 3 Monate bei 50°C gelagert und anschließend analytisch untersucht.The experiment from Example 1 is repeated, instead of of 10 wt .-% glycerol triacetate, the same amount of xylene is added. The sample is also stored for 3 months at 50 ° C and then analyzed analytically.
Gehalt, Gehalt nach Ausgangswert 3 Mon./50°CSalary, salary according to baseline 3 months / 50 ° C
Verbindung I 9,2 Gew.-% 8,6 Gew.-% Verbindung II 4,6 " 3,3 "Compound I 9.2% by weight 8.6% by weight Compound II 4.6 "3.3"
Beispiel 2Example 2
12,5 Gew.-% Fenoxaprop-P-ethyl (I) (= D-Isomer von Fenoxaprop-ethyl) werden in 35 Gew.-% Xylol unter Rühren bei 25-30°C gelöst. Zu der klaren Lösung setzt man 8,8 Gew.-% 1- (2,4-Dichlorphenyl)-3-ethoxycarbonyl-5- trichlormethyl-l,2,4-triazol (II) und danach 10 Gew.-% eines C^-C^g-Fettsäurepolyglykoläthers (mit 8 EO) und 8,7 Gew.-% eines C^-C^ -Fettsäurepolyglykolesters (mit 40 EO) zu und rührt bis zur klaren Lösung. Zu dieser gibt man 5 Gew.-% epoxidiertes Leinöl, 10,0 Gew.-% einer xylolischen Lösung des Ca-Salzes der Dodecylbenzolsulfonsäure und 10 Gew.-% Phosphorsäure-tri-n-butylester und läßt ca. 20 Minuten nachrühren.12.5% by weight of Fenoxaprop-P-ethyl (I) (= D-isomer of Fenoxaprop-ethyl) are dissolved in 35% by weight of xylene with stirring at 25-30 ° C. 8.8% by weight of 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-trichloromethyl-l, 2,4-triazole (II) and then 10% by weight of a C are added to the clear solution ^ -C ^ g fatty acid polyglycol ether (with 8 EO) and 8.7 wt .-% of a C ^ -C ^ fatty acid polyglycol ester (with 40 EO) and stirred until a clear solution. 5% by weight of epoxidized linseed oil, 10.0% by weight of a xylene solution of the Ca salt of dodecylbenzenesulfonic acid and 10% by weight of tri-n-butyl phosphorate are added to this and the mixture is stirred for about 20 minutes.
Ein Teil der Probe wird 3 Monate bei 50°C gelagert und danach analytisch untersucht:Part of the sample is stored for 3 months at 50 ° C and then analyzed analytically:
Gehalt, Gehalt nach Ausgangswert 3 Mon./50°C Verbindung I 11,8 Gew.-% 11,7 Gew.-% Verbindung II 8,2 8,2 "Content, content according to initial value 3 months / 50 ° C compound I 11.8% by weight 11.7% by weight compound II 8.2 8.2 "
Vergleichsbeispiel 2Comparative Example 2
Der Versuch aus Beispiel 2 wird wiederholt, wobei anstelle der 10 Gew.-% Phosphorsäure-tri-n-butylester die gleiche Menge Xylol zugesetzt wird. Die Probe wird ebenfalls 3 Monate bei 50°C gelagert und anschließend analytisch untersucht.The experiment from Example 2 is repeated, the same being used instead of the 10% by weight of tri-n-butyl phosphoric acid Amount of xylene is added. The sample is also stored for 3 months at 50 ° C and then analyzed analytically.
Gehalt, Gehalt nachSalary, salary after
Ausgangswert 3 Mon./50°C Verbindung I 11,6 Gew.-% 9,9 Gew.-% Verbindung II 8,1 " 6,5 "Initial value 3 months / 50 ° C compound I 11.6% by weight 9.9% by weight compound II 8.1 "6.5"
Beispiel 3Example 3
16,5 Gew.-% Fenthiaprop-ethyl (III) werden in 42 Gew.-% Xylol unter Rühren bei 25-30°C gelöst. Zu dieser klaren Lösung setzt man 8,2 Gew.-% 1- (2,4-Dichlor-phenyl)-3- ethoxy-carbonyl-5-trichlormethyl-l,2,4-triazol (II) und danach 5 Gew.-% eines C-j^-C-^g-Fettalkoholpolyglykoläthers (mit 10 EO) und 6,3 Gew.-% eines C-^-C^ -16.5% by weight of fenthiaprop-ethyl (III) are dissolved in 42% by weight of xylene with stirring at 25-30 ° C. 8.2% by weight of 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-trichloromethyl-l, 2,4-triazole (II) and then 5% by weight are added to this clear solution. -% of a C- j ^ -C- ^ g fatty alcohol polyglycol ether (with 10 EO) and 6.3% by weight of a C - ^ - C ^ -
Fettsäurepolyglykolesters (mit 36 EO) zu und rührt bis zur klaren Lösung. Zu dieser gibt man 5 Gew.-% epoxidiertes Leinöl, 5 Gew.-% dodecylbenzolsulfonsaures Calcium und 12 Gew.-% Hexylacetat und läßt ca. 20 Minuten nachrühren.Fatty acid polyglycol ester (with 36 EO) and stir until clear solution. 5% by weight of epoxidized linseed oil, 5% by weight of dodecylbenzenesulfonic acid calcium and 12% by weight of hexyl acetate are added to the mixture, and stirring is continued for about 20 minutes.
Ein Teil der Probe wird 3 Monate bei 50°C gelagert und danach analytisch untersucht:Part of the sample is stored for 3 months at 50 ° C and then analyzed analytically:
Gehalt, Gehalt nachSalary, salary after
Ausgangswert 3 Mon./50°CInitial value 3 months / 50 ° C
Verbindung III 15,6 Gew.-% 15,4 Gew.-%Compound III 15.6% by weight 15.4% by weight
Verbindung II 7,7 " 7,6 "Compound II 7.7 "7.6"
Vergleichsbeispiel 3Comparative Example 3
Der Versuch aus Beispiel 3 wird wiederholt, wobei anstelle der 12 Gew.-% Hexylacetat die gleiche Menge Xylol zugesetzt wird. Die Probe wird ebenfalls 3 Monate bei 50°C gelagert und anschließend analytisch untersucht. Gehalt, Gehalt nach Ausgangswert 3 Mon./50°CThe experiment from Example 3 is repeated, with the same amount of xylene being added instead of the 12% by weight of hexyl acetate. The sample is also stored for 3 months at 50 ° C and then analyzed analytically. Salary, salary according to baseline 3 months / 50 ° C
Verbindung I 15,5 Gew.-% 13,9 Gew.-% Verbindung II 7,6 " 6,0 "Compound I 15.5% by weight 13.9% by weight Compound II 7.6 "6.0"
Beispiel 4Example 4
Man verfährt analog Beispiel 1, setzt als TriazolVerbindung jedoch 1- (2,4-Dichlorphenyl)-3-ethoxycarbonyl-5- dichlormethyl-1,2,4-triazol ein. Es wird ein vergleichbar stabiles Emulsionskonzentrat erhalten.The procedure is analogous to Example 1, but the triazole compound used is 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl-5-dichloromethyl-1,2,4-triazole. A comparable stable emulsion concentrate is obtained.
Beispiel 5Example 5
Man verfährt analog Beispiel 2, setzt jedoch alsThe procedure is analogous to Example 2, but is set as
TriazolVerbindung 1- (2,4-Dichlorphenyl)-3-ethoxycarbonyl- 5- (1,1,2,2-tetrafluorethyl)-1,2,4-triazol ein. Das erhaltene Emulsionskonzentrat ist über 3 Monate bei 50°C stabil und zeigt insbesondere keinen nennenswerten Abbau am Wirkstoffgehalt.Triazole compound 1- (2,4-dichlorophenyl) -3-ethoxycarbonyl- 5- (1,1,2,2-tetrafluoroethyl) -1,2,4-triazole. The emulsion concentrate obtained is stable over 3 months at 50 ° C. and in particular shows no significant degradation in the active substance content.
Biologische BeispieleBiological examples
Die nach den Herstellungsbeispielen erhaltenen Emulsionskonzentrate werden mit Wasser auf dieThe emulsion concentrates obtained according to the preparation examples are mixed with water on the
Anwendungskonzentration verdünnt und in Feldversuchen gegen monokotyle oder dikotyle oder mono- und dikotyle Unkräuter eingesetzt.Diluted application concentration and used in field trials against monocot or dicot or mono- and dicot weeds.
Die biologischen Untersuchungen zeigen, daß weder in der Pflanzenverträglichkeit noch in der herbiziden Wirkung nennenswerte Unterschiede zwischen den Fertigformulierungen und den im Spritztank hergestellten Kombinationen aus den einzelnen Wirkstoffen (Tankmischung) bestehen. The biological studies show that there are no noteworthy differences between the finished formulations and the combinations produced in the spray tank from the individual active ingredients (tank mix), neither in terms of plant tolerance nor in the herbicidal action.

Claims

Patentansprüche:Claims:
1. Flüssige herbizide Mittel auf Basis von1. Liquid herbicidal compositions based on
Emulsionskonzentraten, dadurch gekennzeichnet, daß sieEmulsion concentrates, characterized in that they
a) einen oder mehrere herbizide Phenoxyphenoxy- oder Heteroaryloxy-phenoxy-carbonεäureester,a) one or more herbicidal phenoxyphenoxy- or heteroaryloxy-phenoxy-carboxylic acid esters,
b) ein oder mehrere Verbindungen aus der Gruppe der gegebenenfalls substituierten l-Aryl-3- alkoxycarbony1-5-alkyl-1,2,4- riazole,b) one or more compounds from the group of the optionally substituted 1-aryl-3-alkoxycarbony1-5-alkyl-1,2,4-riazoles,
c) ein oder mehrere Carbonsäure- oder Phosphorsäureester von aliphatischen Mono-/Di- oder Polyalkoholen als stabilisierendes Agens,c) one or more carboxylic acid or phosphoric acid esters of aliphatic mono- / di- or polyalcohols as a stabilizing agent,
d) ein oder mehrere organische Lösungsmittel undd) one or more organic solvents and
e) ein oder mehrere Emulgatoren und gegebenenfalls Netzmittel und übliche Zusatzstoffe enthalten.e) contain one or more emulsifiers and, if appropriate, wetting agents and customary additives.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß sie als Komponente a) gegebenenfalls substituierte Phenoxyphenoxy- , Chinoxalyloxyphenoxy- , Pyridyloxyphenoxy- , Benzoxazolyloxyphenoxy- oder Benzthiazolyloxyphenoxycarbonsäureester enthalten.2. Composition according to claim 1, characterized in that they contain, as component a) optionally substituted phenoxyphenoxy, quinoxalyloxyphenoxy, pyridyloxyphenoxy, benzoxazolyloxyphenoxy or benzothiazolyloxyphenoxycarboxylic acid esters.
Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie als Komponente b)Agent according to Claim 1 or 2, characterized in that it is used as component b)
1- (2,4-Dichlorphenyl)-3- (C1-C4-alkoxy)carbonyl-5- halogenalkyl-1,2,4- riazol-Verbindungen enthalten.Contain 1- (2,4-dichlorophenyl) -3- (C 1 -C 4 alkoxy) carbonyl-5-haloalkyl-1,2,4-riazole compounds.
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie als Komponente c) Ester aus C2-C5-Carbonsäuren oder Phosphorsäure und linearen oder verzweigten aliphatischen ~-2" -- .2~Alkoholen,-Diolen oder-Polyolen enthalten. 5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie als Lösungsmittel Toluol, Xylole, höhersiedende Aromatenfraktionen, Methylnaphthaline oder Cyclohexanon enthalten.4. Composition according to one or more of claims 1 to 3, characterized in that it contains as component c) esters of C2-C5-carboxylic acids or phosphoric acid and linear or branched aliphatic ~ -2 "- .2 ~ alcohols, diols or - Contain polyols. 5. Composition according to one or more of claims 1 to 4, characterized in that they contain toluene, xylenes, higher-boiling aromatic fractions, methylnaphthalenes or cyclohexanone as solvents.
6. Mittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie als Komponente e) übliche Emulgatoren und Netzmittel aus der Gruppe, enthaltend Alkylbenzolsulfonate, Fettsäurepolyglykolester, Alkylphenol- und Alkanol¬ polyglykolether, enthalten.6. Composition according to one or more of claims 1 to 5, characterized in that they contain, as component e), customary emulsifiers and wetting agents from the group comprising alkylbenzenesulfonates, fatty acid polyglycol esters, alkylphenol and alkanol polyglycol ethers.
7. Mittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie 5-50 Gew.-% der Komponenten a) und b), 2-20 Gew.-% der Komponente c),7. Composition according to one or more of claims 1 to 6, characterized in that it contains 5-50% by weight of components a) and b), 2-20% by weight of component c),
5-40 Gew.-% Lösungsmittel, 10-30 Gew.-% Emulgatoren und Netzmittel enthalten.Contain 5-40 wt .-% solvent, 10-30 wt .-% emulsifiers and wetting agents.
8. Mittel nach Anspruch 7, dadurch gekennzeichnet, daß 20-35 Gew.-% Komponenten a) und b),8. Composition according to claim 7, characterized in that 20-35 wt .-% components a) and b),
5-15 Gew.-% Komponente c), 10-25 Gew.-% Lösungsmittel, 15-25 Gew.-% Emulgatoren und Netzmittel enthalten sind.5-15 wt .-% component c), 10-25 wt .-% solvent, 15-25 wt .-% emulsifiers and wetting agents are included.
9. Verfahren zur Herstellung eines nach einem oder mehreren der Ansprüche 1 bis 8 definierten herbiziden Mittels, dadurch gekennzeichnet, daß man die Komponenten a) bis e) bei 10 bis 60°C mischt, bis sich eine homogene Lösung aller Komponenten gebildet hat.9. A process for the preparation of a herbicidal composition as claimed in one or more of claims 1 to 8, characterized in that components a) to e) are mixed at 10 to 60 ° C until a homogeneous solution of all components has formed.
10. Verwendung der Mittel nach einem oder mehreren der Ansprüche 1 bis 8 zur Herstellung von wäßrigen herbiziden Emulsionen. 10. Use of the composition according to one or more of claims 1 to 8 for the preparation of aqueous herbicidal emulsions.
EP19900915442 1989-10-28 1990-10-24 Selective herbicides Withdrawn EP0497806A1 (en)

Applications Claiming Priority (2)

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DE3935977 1989-10-28
DE19893935977 DE3935977A1 (en) 1989-10-28 1989-10-28 SELECTIVE HERBICIDES

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DK0514769T3 (en) * 1991-05-18 1997-02-10 Hoechst Schering Agrevo Gmbh
WO1994026108A1 (en) * 1993-05-10 1994-11-24 Zeneca Limited Safening pyridyloxyphenoxy propionic acid herbicides
AUPN265895A0 (en) 1995-04-28 1995-05-25 Risk Management Resources Pty Ltd Control wheel assembly for trolleys
JP3855321B2 (en) * 1996-11-01 2006-12-06 住友化学株式会社 Agrochemical composition
DE19913036A1 (en) * 1999-03-23 2000-09-28 Aventis Cropscience Gmbh Liquid preparations and surfactant / solvent systems
JP4543738B2 (en) * 2004-05-11 2010-09-15 住友化学株式会社 Agricultural emulsion

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DE3203779A1 (en) * 1982-02-04 1983-08-11 Hoechst Ag, 6230 Frankfurt HERBICIDAL AGENTS
GR78909B (en) * 1982-08-13 1984-10-02 Sipcam Spa
DE3525205A1 (en) * 1984-09-11 1986-03-20 Hoechst Ag, 6230 Frankfurt PLANT PROTECTIVE AGENTS BASED ON 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE
DD251276A5 (en) * 1985-06-04 1987-11-11 Rhone-Poulenc Agrochimie,Fr STABILIZED LIQUID HERBICIDES COMPOSITIONS BASED ON M-BIS CARBANATES AND THEIR USE
ES2045184T3 (en) * 1987-10-02 1994-01-16 Ciba Geigy Ag DERIVATIVES OF THE ACID 1,5-DIFENIL-1,2,4-TRIAZOL-3-CARBOXILICO FOR THE PROTECTION OF CROP PLANTS AGAINST THE PHYTOTOXIC ACTION OF HERBICIDES.
DE3817192A1 (en) * 1988-05-20 1989-11-30 Hoechst Ag PLANT-PROTECTIVE AGENTS CONTAINING 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE

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AU642920B2 (en) 1993-11-04
AU6549490A (en) 1991-05-31
DE3935977A1 (en) 1991-05-02
IE903870A1 (en) 1991-05-08
CA2072104A1 (en) 1991-04-29

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