Herbicidal mixtures.
Abstract
Fliessfähige, herbizide Zusammensetzungen, die eine Wirkstoffkombination aus Glyphosate und einem Triazinherbizid enthalten, bilden stabile wässrige Suspensionen, wenn die Tensidkomponenten der Zubereitung aus einem anionischen Tensid aus der Reihe der hierin beschriebenen Formeln III, IV oder V und einem kationischen Tensid der Formel VI bestehen.

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36 claims: 1 independent, 35 dependent
- 1Fliessfähige herbizide Wirkstoffsuspension enthaltend als aktive Komponenten einerseits N-Phosphonomethylglycin oder dessen wasserlösliches Salz und andererseits ein Triazinherbizid, dadurch gekennzeichnet, dass sie 5 bis 40 Gewichts-% N-Phosphonomethylglycin der Formel I oder dessen wasserlösliches Salz; 8 bis 50 Gewichts.-% eines Triazinherbizids der Formel II worin R¹ Chlor, Methoxy, Methylthio oder Aethylthio, R² und R⁴ unabhängig voneinander Wasserstoff oder C₁-C₄-Alkyl, R³ C₁-C₄-Alkyl und R⁵ C₁-C₅-Alkyl, C₃-C₄-Cycloalkyl oder durch Cyan oder Methoxy substituiertes C₁-C₄-Alkyl bedeuten; 0,1 bis 10 Gewichts-% eines anionischen Tensids der Formel III worin R⁶ einen Rest X und Y unabhängig voneinander eine Aethylen- oder Propylenbrücke, R⁷ einen geradkettigen oder verzweigten C₆-C₁₄-Alkylrest, Z Wasserstoff oder einen unter R⁶ definierten Rest, m und n unabhängig voneinander Zahlen von 2 bis 25, r eine Zahl von 1 bis 9, und M ⊕ ein Proton, ein Alkalimetallkation oder ein Aequivalent eines Erdalkalimetallkations bedeuten; welches man erhält, indem man in an sich bekannter Weise Monoalkylphenole der Formel mit Formaldehyd im Molverhältnis 2:1 bis 10:9 in Gegenwart von sauren Katalysatoren zu mehrkernigen Novolakharzen kondensiert, diese in Gegenwart von alkalischen Katalysatoren mit 2 bis 25 Mol Alkylenoxid je Mol eingesetzten Monoalkylphenols umsetzt, die freien Hydroxylgruppen der erhaltenen Oxalkylierungsprodukte ganz oder teilweise mit Maleinsäureanhydrid verestert und danach die erhaltenen Maleinsäurehalbester in wässriger Phase mit Salzen der schwefligen Säure zu den Sulfobernsteinsäurehalbestern der Formel III umsetzt;oder eines anionischen Tensids der Formel IV worin R⁸ einen Rest der Formel bedeutet, R⁹ die gleiche Bedeutung wie R⁸ hat oder für Wasserstoff steht und A ⊕ ein Proton oder ein Alkalimetall- oder Triäthanolammoniumkation bedeutet, wobei s für eine Zahl von 1 bis 4, t für eine Zahl von 2 bis 40 und R¹⁰ für Wasserstoff, Styryl oder C₃-C₁₀-Alkyl stehen;oder eines anionischen Tensids der Formel V worin R¹¹ für C₈-C₃₅-Alkyl und B ⊕ für ein Alkalimetallkation oder ein Ammoniumkation der Formel worin R¹², R¹³, R¹⁴ und R¹⁵ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, oder C₁-C₄-Hydroxyalkyl bedeuten, stehen;0,1 bis 10 Gewichts-% eines kationischen Tensids der Formel VI worin R¹⁶ und R¹⁷ unabhängig voneinander C₁-C₄-Alkyl, R¹⁸ C₁-C₃₅-Alkyl, Phenyl, Benzyl oder ein- oder mehrfach ungesättigtes C₃-C₃₅-Alkenyl;R¹⁹ C₈-C₃₅-Alkyl, Phenyl, Benzyl oder ein- oder mehrfach ungesättigtes C₃-C₃₅-Alkenyl, und E ⊖ ein Halogenanion, ein Nitratanion oder ein Aequivalent eines Sulfat- oder Phosphatanions bedeuten;und ad 100 Gewichts-% Wasser enthält.
- 2Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 5 bis 40 Gewichts-% N-Phosphonomethylglycin der Formel I oder dessen Isopropylammoniumsalz; 8 bis 50 Gewichts.-% eines Triazinherbizids der Formel II worin R¹ Chlor, Methoxy, Methylthio oder Aethylthio, R² und R⁴ unabhängig voneinander Wasserstoff oder C₁-C₄-Alkyl, R³ C₁-C₄-Alkyl und R⁵ C₁-C₅-Alkyl, C₃-C₄-Cycloalkyl oder durch Cyan oder Methoxy substituiertes C₁-C₄-Alkyl bedeuten; 0,1 bis 10 Gewichts-% eines anionischen Tensids der Formel III worin R⁶ einen Rest X und Y unabhängig voneinander eine Aethylen- oder Propylenbrücke, R⁷ einen geradkettigen oder verzweigten C₆-C₁₄-Alkylrest, Z Wasserstoff oder einen unter R⁶ definierten Rest, m und n unabhängig Zahlen von 2 bis 25, r eine Zahl von 1 bis 9, und M ⊕ ein Proton, ein Alkalimetallkation oder ein Aequivalent eines Erdalkalimetallkations bedeuten; welches man erhält, indem man in an sich bekannter Weise Monoalkylphenole der Formel mit Formaldehyd im Molverhältnis 2:1 bis 10:9 in Gegenwart von sauren Katalysatoren zu mehrkernigen Novolakharzen kondensiert, diese in Gegenwart von alkalischen Katalysatoren mit 2 bis 25 Mol Alkylenoxid je Mol eingesetzten Monoalkylphenols umsetzt, die freien Hydroxylgruppen der erhaltenen Oxalkylierungsprodukte ganz oder teilweise mit Maleinsäureanhydrid verestert und danach die erhaltenen Maleinsäurehalbester in wässriger Phase mit Salzen der schwefligen Säure zu den Sulfobernsteinsäurehalbestern der Formel III umsetzt;oder eines anionischen Tensids der Formel IV worin R⁸ einen Rest der Formel bedeutet, R⁹ die gleiche Bedeutung wie R⁸ hat oder für Wasserstoff steht und A ⊕ ein Proton oder ein Alkalimetall- oder Triäthanolammoniumkation bedeutet, wobei s für eine Zahl von 1 bis 4, t für eine Zahl von 2 bis 40 und R¹⁰ für Wasserstoff, Styryl oder C₃-C₁₀-Alkyl stehen;oder eines anionischen Tensids der Formel V worin R¹¹ für C₈-C₃₅-Alkyl und B ⊕ für ein Alkalimetallkation oder ein Ammoniumkation der Formel worin R¹², R¹³, R¹⁴ und R¹⁵ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, oder C₁-C₄-Hydroxyalkyl bedeuten, stehen;0,1 bis 10 Gewichts-% eines kationischen Tensids der Formel VI worin R¹⁶ und R¹⁷ unabhängig voneinander C₁-C₄-Alkyl, R¹⁸ C₁-C₃₅-Alkyl, Phenyl, Benzyl oder ein- oder mehrfach ungesättigtes C₃-C₃₅-Alkenyl;R¹⁹ C₈-C₃₅-Alkyl, Phenyl, Benzyl oder ein- oder mehrfach ungesättigtes C₃-C₃₅-Alkenyl, und E ⊖ ein Halogenanion, ein Nitratanion oder ein Aequivalent eines Sulfat- oder Phosphatanions bedeuten;und ad 100 Gewichts-% Wasser enthält.
- 3Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als eine herbizide Wirkstoffkomponente ein wasserlösliches Alkylammoniumsalz oder Alkanolammoniumsalz des N-Phosphonomethylglycins enthält.
- 4Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie zusätzlich 0,01 bis 5 Gewichts-% eines wasserlöslichen oder in Wasser quellfähigen Verdickungsmittels enthält.
- 5Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie zusätzlich 0,01 bis 5 Gewichts-% eines wasserlöslichen oder in Wasser quellfähigen Verdickungsmittels, 0,01 bis 5 Gewichts-% eines schaumhemmenden Mittels und 0 bis 25 Gewichts-% eines Antifrostmittels enthält.
- 6Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als eine herbizide Wirkstoffkomponente das Isopropylammoniumsalz des N-Phosphonomethylglycins enthält.
- 7Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als Wirkstoffe einerseits das Isopropylammoniumsalz des N-Phosphonomethylglycins und andererseits ein Chlortriazin der Formel II enthält, worin R¹ für Chlor steht.
- 8Wirkstoffsuspension gemäss Anspruch 7, dadurch gekennzeichnet, dass das Chlortriazin aus der Reihe 2,4-bis-Aethylamino-6-chlor-1,3,5-triazin, 2-Aethylamino-4-isopropylamino-6-chlor-1,3,5-triazin, 2-Aethylamino-4-(1-cyan-1-methyläthylamino)-6-chloro-1,3,5-triazin, 2-Cyclopropylamino-4-isopropylamino-6-chlor-1,3,5-triazin, 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 2,4-bis-Isopropylamino-6-chlor-1,3,5-triazin, 2-Isopropylamino-4-(3-methoxypropylamino)-6-chlor-1,3,5-triazin, 2,4-bis-Diäthylamino-6-chlor-1,3,5-triazin, 2-Aethylamino-4-diäthylamino-6-chlor-1,3,5-triazin, oder 2-Aethylamino-4-sek.butylamino-6-chlor-1,3,5-triazin ausgewählt ist.
- 9Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als anionisches Tensid eine Verbindung der Formel III enthält.
- 10Wirkstoffsuspension gemäss Anspruch 6, dadurch gekennzeichnet, dass sie 10 bis 25 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 25 bis 45 Gewichts-% eines Triazins der Formel II, 0,3 bis 5 Gewichts-% eines anionischen Tensids der Formeln III, IV oder V und 0,3 bis 5 Gewichts-% eines kationischen Tensids der Formel VI enthält.
- 11Wirkstoffsuspension gemäss Anspruch 10, dadurch gekennzeichnet, dass sie als anionisches Tensid eine Verbindung der Formel III enthält.
- 12Wirkstoffsuspension gemäss Anspruch 6, dadurch gekennzeichnet, dass sie 13 bis 25 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 20 bis 35 Gewichts-% eines Triazins der Formel II, 0,3 bis 3 Gewichts-% eines anionischen Tensids der Formeln III, IV oder V und 0,3 bis 3 Gewichts-% eines kationischen Tensids der Formel VI enthält.
- 13Wirkstoffsuspension gemäss Anspruch 12, dadurch gekennzeichnet, dass sie als anionisches Tensid eine Verbindung der Formel III enthält.
- 14Wirkstoffsuspension gemäss Anspruch 12, dadurch gekennzeichnet, dass sie ein anionisches Tensid der Formel III und als Triazin der Formel II die Verbindung 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin enthält.
- 15Wirkstoffsuspension gemäss Anspruch 12, dadurch gekennzeichnet, dass sie zusätzlich 0,05 bis 0,2 Gewichts-% eines wasserlöslichen oder in Wasser quellfähigen Verdickungsmittels, 0,05 bis 2 Gewichts-% eines schaumhemmenden Mittels, 0,05 bis 0,2 Gewichts-% eines Konservierungsmittels und 0 bis 10 Gewichts-% eines Antifrostmittels enthält.
- 16Wirkstoffsuspension gemäss Anspruch 14, dadurch gekennzeichnet, dass sie als Verdickungsmittel Polysaccharid, als schaumhemmendes Mittel Silikonöl, als Konservierungsmittel Formaldehyd oder 1,2-Benzisothiazol-3-on und als Antifrostmittel Aethylenglykol oder Propylenglykol enthält.
- 17Wirkstoffsuspension gemäss Anspruch 9, dadurch gekennzeichnet, dass in der Formel III des anionischen Tensids X und Y jeweils für Aethylenbrücken, Z für R⁶, M ⊕ für ein Natriumkation, m und n unabhängig voneinander für Zahlen von 4 bis 11 und r fur eine Zahl von 1 bis 3 stehen.
- 18Wirkstoffsuspension gemäss Anspruch 17, dadurch gekennzeichnet, dass m und n die Zahl 6 und r die Zahl 2 bedeuten.
- 19Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass in der Formel IV des anionischen Tensids R¹⁰ für Wasserstoff oder Styryl, A ⊕ für ein Triäthanolammoniumkation, s für eine Zahl von 1 bis 3 und t für eine Zahl von 10 bis 30 stehen.
- 20Wirkstoffsuspension gemäss Anspruch 19, dadurch gekennzeichnet, dass das anionische Tensid der Formel IV durch ein Gemisch von Mono- und Di-(tristyrylphenol-octadecaglykoläther)-phosphorsäureester-triäthanolammoniumsalzen verkörpert sind.
- 21Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass in der Formel V des anionischen Tensids B ⊕ für das Triäthanolammoniumkation und R¹¹ für C₉-C₁₅-Alkyl stehen.
- 22Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass in der Formel IV des anionischen Tensids R¹⁰ für C₃-C₁₅-Alkyl, A ⊕ für ein Alkalimetallkation, s für die Zahl eins und t für eine Zahl von 5 bis 13 stehen.
- 23Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass das anionische Tensid der Formel IV durch ein Gemisch von Mono- und Di-(nonylphenol-nonaglykoläther)-phosphorsäureester-Kaliumsalzen verkörpert wird.
- 24Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass in der Formel VI des kationischen Tensids E ⊖ für ein Halogenanion, R¹⁶, R¹⁷ und R¹⁸ für Methyl und R¹⁹ für C₉-C₁₅-Alkyl stehen.
- 25Wirkstoffsuspension gemäss Anspruch 24, dadurch gekennzeichnet, dass das kationische Tensid der Formel VI durch Dodecyltrimethylammoniumchlorid verkörpert wird.
- 26Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass es 13 bis 25 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 20 bis 35 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 0,3 bis 3 Gewichts-% eines anionichen Tensids der Formel III gemäss Anspruch 16, oder eines Mono- und Di-(tristyrylphenol-octadecaglykoläther)-phosphorsäureester-triäthanolammoniumsalz-Gemisches, oder eines Mono- und Di-(nonylphenol-nonaglykoläther)-phosphorsäureester-Kaliumsalz-Gemisch, oder Dodecylbenzolsulfonsäure-triäthanolammoniumsalz, 0,3 bis 3 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,05 bis 0,2 Gewichts-% Polysaccharid, 0,05 bis 2,0 Gewichts-% Silikonöl, 0,05 bis 0,2 Gewichts-% 1,2-Benzisothiazol-3-on oder einer 37 %igen Formaldehydlösung, 0 bis 10 Gewichts-% Aethylenglykol oder Propylenglykol, und ad 100 Gewichts-% Wasser enthält.
- 27Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 21 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 30 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 1,5-Gewichts-% anionisches Tensid gemäss Anspruch 16, 0,5 Gewichts-% Dodecyltrimethylammoniumchlorid, 1,5 Gewichts-% Silikonöl, 0,13 Gewichts-% Polysaccharid, 0,13 Gewichts-% 37 %ige Formaldehydlösung und ad 100 Gewichts-% Wasser enthält.
- 28Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 14,5 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 30 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 1,6 Gewichts-% anionisches Tensid gemäss Anspruch 16, 0,5 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,8 Gewichts-% Silikonöl, 0,1 Gewichts-% Polysaccharid, 0,1 Gewichts-% 37 %ige Formaldehydlösung und ad 100 Gewichts-% Wasser enthält.
- 29Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 18 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 31 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 1,6 Gewichts-% anionisches Tensid gemäss Anspruch 16, 0,5 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,8 Gewichts-% Silikonöl, 0,1 Gewichts-% Polysaccharid, 0,1 Gewichts-% 37 %ige Formaldehydlösung und ad 100 Gewichts-% Wasser enthält.
- 30Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 21 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 30 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 2 Gewichts-% Mono- und Di-(tristyrylphenol-octadecaglykoläther)-phosphorsäureester-triäthanolammoniumsalz-Gemisch, 0,75 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,1 Gewichts-% Silikonöl, 0,15 Gewichts-% Polysaccharid, 0,10 Gewichts-% 1,2-Benzisothiazol-3-on und ad 100 Gewichts-% Wasser enthält.
- 31Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 21 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 30 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 2 Gewichts-% Mono- und Di-(nonylphenol-nonaglykoläther)-phosphorsäureester-Kaliumsalz-Gemische, 0,75 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,1 Gewichts-% Silikonöl, 0,15 Gewichts-% Polysaccharid, 0,10 Gewichts-% 1,2-Benzisothiazol-3-on und ad 100 Gewichts-% Wasser enthält.
- 32Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 21 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 30 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 0,75 Gewichts-% Dodecylbenzolsulfonsäure-triäthanolammoniumsalz, 0,9 Gewichts-% Dodecyltrimethylammoniumchlorid, 0,1 Gewichts-% Silikonöl, 0,15 Gewichts-% Polysaccharid, 0,1 Gewichts-% 1,2-Benzisothiazol-3-on und ad 100 Gewichts-% Wasser enthält.
- 33Wirkstoffsuspension gemäss Anspruch 1, dadurch gekennzeichnet, dass sie 21 Gewichts-% Isopropylammoniumsalz des N-Phosphonomethylglycins, 26 Gewichts-% 2-Aethylamino-4-tert.butylamino-6-chlor-1,3,5-triazin, 1,5 Gewichts-% anionisches Tensid gemäss Anspruch 16, 0,5 Gewichts-% Dodecyltrimethylammoniumchlorid, 1,4 Gewichts-% Silikonöl, 0,15 Gewichts-% Polysaccharid, 0,15 Gewichts-% 37 %ige Formaldehydlösung und ad 100 Gewichts-% Wasser enthält.
- 34Verwendung der Wirkstoffsuspension gemäss Anspruch 1 zur Bekämpfung von Unkräuter in mehrjährigen Kulturen.
- 35Verwendung gemäss Anspruch 34, dadurch gekennzeichnet, dass es sich bei den behandelten Kulturen im Baumkulturen handelt.
- 36Verfahren zur Bekämpfung von Unkräutern in mehrjährigen Kulturen, dadurch gekennzeichnet, dass man auf das Kulturland eine wirksame Menge der Wirkstoffsuspension gemäss Anspruch 1 ausbringt.
Independent claims36
40 paragraphs, as filed
The present invention relates to a flowable, herbicidal composition in the form of an aqueous suspension which contains an active ingredient mixture of glyphosate and a triazine herbicide and a new surfactant mixture.
Glyphosates and triazine herbicides, processes for their preparation and their action as herbicides have long been known from the literature.
Mixtures of these two classes of active substances are commercially available as aqueous dispersions. The active ingredient combinations contained therein differ in the quantitative composition of the individual active ingredients depending on the application culture, type, climate and regional weed population.
With the customary surface-active formulation auxiliaries used to date, such as dispersants, emulsifiers and surfactants, a low-concentration combination of the two active ingredient components is achieved. At higher active substance concentrations, in particular of glyphosate or its salt, the formulations obtained are unsatisfactory in terms of their stability and manageability.
There is therefore a need to have a formulation option which allows all the biologically and technologically desired changes in the active ingredient content of a flowable, higher-concentration suspension, in particular an increase in the glyphosate content. From an economic point of view, a highly concentrated agent is advantageous because it saves storage, transport and packaging costs.
It is therefore proposed according to the invention to combine a flowable, herbicidal composition in the form of an active ingredient suspension which, on the one hand, contains N-phosphonomethylglycine or its water-soluble salt and, on the other hand, a triazine herbicide as active components, in such a way that it 5 to 40% by weight of N-phosphonomethylglycine of the formula I.<chemistry id="chem0001" num="0001"><img file="EP0357553A2_D0001.tif" /></chemistry> or its water-soluble salt; 8 to 50% by weight of a triazine herbicide of the formula II<chemistry id="chem0002" num="0002"><img file="EP0357553A2_D0002.tif" /></chemistry> wherein R1 chlorine, methoxy, methylthio or ethylthio, R² and R⁴ independently of one another are hydrogen or C₁-C₄-alkyl, R³ C₂-C₄ alkyl and R⁵ is C₁-C₅-alkyl, C₃-C₄-cycloalkyl or C₁-C₄-alkyl substituted by cyan or methoxy; 0.1 to 10% by weight of an anionic surfactant of the formula III<chemistry id="chem0003" num="0003"><img file="EP0357553A2_D0003.tif" /></chemistry> wherein R⁶ a rest<chemistry id="chem0004" num="0004"><img file="EP0357553A2_D0004.tif" /></chemistry> X and Y independently of one another are an ethylene or propylene bridge, R⁷ is a straight-chain or branched C₆-C₁₄ alkyl radical, Z is hydrogen or a radical defined under R⁶,<u style="single">m</u> and <u style="single">n</u> independently of one another numbers from 2 to 25,<u style="single">r</u> a number from 1 to 9, and M<sup>⊕</sup> is a proton, an alkali metal cation or an equivalent of an alkaline earth metal cation; which is obtained by using monoalkylphenols of the formula in a manner known per se<chemistry id="chem0005" num="0005"><img file="EP0357553A2_D0005.tif" /></chemistry> condensed with formaldehyde in a molar ratio of 2: 1 to 10: 9 in the presence of acidic catalysts to give polynuclear novolak resins, which are reacted with 2 to 25 moles of alkylene oxide per mole of monoalkylphenol used in the presence of alkaline catalysts, the free hydroxyl groups of the oxyalkylation products obtained are wholly or partially esterified with maleic anhydride and then the maleic acid half-esters obtained are reacted in an aqueous phase with salts of sulfurous acid to give the sulfosuccinic acid half-esters of the formula III; or an anionic surfactant of formula IV<chemistry id="chem0006" num="0006"><img file="EP0357553A2_D0006.tif" /></chemistry> wherein R⁸ is a radical of the formula<chemistry id="chem0007" num="0007"><img file="EP0357553A2_D0007.tif" /></chemistry> means R⁹ has the same meaning as R⁸ or represents hydrogen and A<sup>⊕</sup> means a proton or an alkali metal or triethanolammonium cation, wherein <u style="single">s</u> for a number from 1 to 4, <u style="single">t</u> represent a number from 2 to 40 and R¹⁰ represents hydrogen, styryl or C₃-C₁₀ alkyl; or an anionic surfactant of formula V<chemistry id="chem0008" num="0008"><img file="EP0357553A2_D0008.tif" /></chemistry> wherein R¹¹ for C₈-C₃₅-alkyl and B<sup>⊕</sup> for an alkali metal cation or an ammonium cation of the formula<chemistry id="chem0009" num="0009"><img file="EP0357553A2_D0009.tif" /></chemistry> wherein R¹², R¹³, R¹⁴ and R¹⁵ independently represent hydrogen, C₁-C₄-alkyl, or C₁-C₄-hydroxyalkyl; 0.1 to 10% by weight of a cationic surfactant of the formula VI<chemistry id="chem0010" num="0010"><img file="EP0357553A2_D0010.tif" /></chemistry> wherein R¹⁶ and R¹⁷ independently of one another C₁-C₄-alkyl, R¹⁸ C₁-C₃₅ alkyl, phenyl, benzyl or mono- or polyunsaturated C₃-C₃₅ alkenyl; R¹⁹ C₈-C₃₅-alkyl, phenyl, benzyl or mono- or polyunsaturated C₃-C₃₅-alkenyl, and E<sup>⊖</sup> is a halogen anion, a nitrate anion or an equivalent of a sulfate or phosphate anion; and contains 100% water by weight.
Preferred herbicidal compositions are composed such that they 5 to 40% by weight of N-phosphonomethylglycine of the formula I.<chemistry id="chem0011" num="0011"><img file="EP0357553A2_D0011.tif" /></chemistry> or its isopropylammonium salt; 8 to 50% by weight of a triazine herbicide of the formula II<chemistry id="chem0012" num="0012"><img file="EP0357553A2_D0012.tif" /></chemistry> wherein R1 chlorine, methoxy, methylthio or ethylthio, R² and R⁴ independently of one another are hydrogen or C₁-C₄-alkyl, R³ C₁-C₄-A lkyl and R⁵ is C₁-C₅-alkyl, C₃-C₄-cycloalkyl or C₁-C₄-alkyl substituted by cyan or methoxy; 0.1 to 10% by weight of an anionic surfactant of the formula III<chemistry id="chem0013" num="0013"><img file="EP0357553A2_D0013.tif" /></chemistry> wherein R⁶ a rest<chemistry id="chem0014" num="0014"><img file="EP0357553A2_D0014.tif" /></chemistry> X and Y independently of one another are an ethylene or propylene bridge, R⁷ is a straight-chain or branched C₆-C₁₄ alkyl radical, Z is hydrogen or a radical defined under R⁶,<u style="single">m</u> and <u style="single">n</u> independently of one another numbers from 2 to 25,<u style="single">r</u> a number from 1 to 9, and M<sup>⊕</sup> is a proton, an alkali metal cation or an equivalent of an alkaline earth metal cation; which is obtained by using monoalkylphenols of the formula in a manner known per se<chemistry id="chem0015" num="0015"><img file="EP0357553A2_D0015.tif" /></chemistry> condensed with formaldehyde in a molar ratio of 2: 1 to 10: 9 in the presence of acidic catalysts to give polynuclear novolak resins, which are reacted with 2 to 25 moles of alkylene oxide per mole of monoalkylphenol used in the presence of alkaline catalysts, the free hydroxyl groups of the oxyalkylation products obtained are wholly or partially esterified with maleic anhydride and then the maleic acid half-esters obtained are reacted in an aqueous phase with salts of sulfurous acid to give the sulfosuccinic acid half-esters of the formula III; or an anionic surfactant of formula IV<chemistry id="chem0016" num="0016"><img file="EP0357553A2_D0016.tif" /></chemistry> wherein R⁸ is a radical of the formula<chemistry id="chem0017" num="0017"><img file="EP0357553A2_D0017.tif" /></chemistry> means R⁹ has the same meaning as R⁸ or represents hydrogen and A<sup>⊕</sup> means a proton or an alkali metal or triethanolammonium cation, wherein <u style="single">s</u> for a number from 1 to 4, <u style="single">t</u> represent a number from 2 to 40 and R¹⁰ represents hydrogen, styryl or C₃-C₁₀ alkyl; or an anionic surfactant of formula V<chemistry id="chem0018" num="0018"><img file="EP0357553A2_D0018.tif" /></chemistry> wherein R¹¹ for C₈-C₃₅-alkyl and B<sup>⊕</sup> for an alkali metal cation or an ammonium cation of the formula<chemistry id="chem0019" num="0019"><img file="EP0357553A2_D0019.tif" /></chemistry> wherein R¹², R¹³, R¹⁴ and R¹⁵ independently represent hydrogen, C₁-C₄-alkyl, or C₁-C₄-hydroxyalkyl; 0.1 to 10% by weight of a cationic surfactant of the formula VI<chemistry id="chem0020" num="0020"><img file="EP0357553A2_D0020.tif" /></chemistry> wherein R¹⁶ and R¹⁷ independently of one another C₁-C₄-alkyl, R¹⁸ C₁-C₃₅ alkyl, phenyl, benzyl or mono- or polyunsaturated C₃-C₃₅ alkenyl; R¹⁹ C₈-C₃₅-alkyl, phenyl, benzyl or mono- or polyunsaturated C₃-C₃₅-alkenyl, and E<sup>⊖</sup> is a halogen anion, a nitrate anion or an equivalent of a sulfate or phosphate anion; and ad 100% water by weight.
In the definitions of the radicals R² to R⁵ and R¹² to R¹⁷, alkyl represents methyl, ethyl, n-propyl, i-propyl, the four isomeric butyl radicals and the isomeric pentyl radicals. Cycloalkyl radicals are cyclopropyl and cyclobutyl. Alkyl substituted by cyan or methoxy is in particular 1-cyan-1-methylethyl or 3-methoxypropyl. Hydroxyalkyl is preferably 2-hydroxyethyl. Alkyl groups with up to 35 carbon atoms, as they are mainly used in the definitions of the surfactants of formulas III, IV, V and VI, or the radicals R⁷, R¹⁰, R¹¹, R¹⁸ and R¹⁹, refer to branched and straight-chain alkyl substituents.
Examples are n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl, but also their isomers with branched chains such as trimethylnonyl, tetramethylnonyl, dimethylundecyl and dipropylhexyl.
The number of carbon atoms is an average. The numbers, which by<u style="single">m</u>, <u style="single">n</u>, <u style="single">r</u>, <u style="single">s</u> and <u style="single">t</u> are embodied, also give average values of the degree of alkylation, alkyleneoxylation or polymerization.
Examples of substituted phenyl groups as in the definitions of R⁸ or formula V are 4-nonylphenyl; 2,4,6-tributylphenyl; 2,4,6-tristyrylphenyl; 2,4-dinonylphenyl; 2,4,6-tripentylphenyl; 2,4-distyrylphenyl; 4-styrylphenyl; 2,3,4,6-tetrabutylphenyl; 4-decylphenyl; Dodecylphenyl; 4-heptylphenyl; 4-pentylphenyl; 2,4-dihexylphenyl; 2,4-dioctylphenyl; 4-octylphenyl; 4-hexylphenyl; 2,4-dipentylphenyl and 2,4,6-tripentylphenyl.
Examples of active substances of the formula II which can be formulated in the compositions according to the invention are: 2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine (Ametryn), 2-ethylamino-4-tert.butylamino-6-methylthio-1,3,5-triazine (Terbutryne), 2- Ethylamino-4-tert-butylamino-6-methoxy-1,3,5-triazine (terbumetone), 2,4-ethylamino-6-methylthio-1,3,5-triazine (Simetryne), 2,4-bis- Isopropylamino-6-methoxy-1,3,5-triazine (prometon), 2,4-bis-isopropylamino-6-methylthio-1,3,5-triazine (prometryne), 2-isopropylamino-4-methylamino-6- methylthio-1,3,5-triazine (Desmetryne), 2-isopropylamino-4- (3-methoxypropylamino) -6-methylthio-1,3,5-triazine (Methoprotryne), 2-ethylthio-4,6-bis-isopropylamino-1,3,5-triazine (Dipropetryn), 2,4-bis-diethylamino-6-chloro-1,3,5-triazine (chlorazine), 2-ethylamino-4-sec-butylamino-6-methoxy-1,3,5-triazine (secbumetone), 2- Ethylamino-4- (1,2-dimethylpropylamino) -6-methylthio-1,3,5-triazine (dimethametryn), 2,4-bis-ethylamino-6-chloro-1,3,5-triazine (simazine), 2-ethylamino-4-isopropylamino-6-chloro-1,3,5-triazine (atrazine), 2-ethylamino-4- (1-cyan-1-methylethylamino) -6-chloro-1,3,5-triazine (cyanazine), 2-cyclopropylamino-4-isopropylamino-6-chloro-1,3,5-triazine (Cyprazine), 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine (terbutylazine), 2,4-bis-isopropylamino-6-chloro-1,3,5-triazine (propazine ), 2-isopropylamino-4- (3-methoxypropylamino-6-chloro-1,3,5-triazine (mesoprazine), 2-tert-butylamino-4-methylamino-6-chloro-1,3,5-triazine , 2-ethylamino-4-diethylamino-6-chloro-1,3,5-triazine (trietazines) and 2-ethylamino-4-sec-butylamino-6-chloro-1,3,5-triazine (sebuthylazine).
Among the triazine active ingredients, chlorotriazines (R 1 stands for chlorine) are preferred. Such an active ingredient is preferably from the series 2,4-bis-ethylamino-6-chloro-1,3,5-triazine, 2-ethylamino-4-isopropylamino-6-chloro-1,3,5-triazine, 2- Ethylamino-4- (1-cyano-1-methylethylamino) -6-chloro-1,3,5-triazine, 2-cyclopropylamino-4-isopropylamino-6-chloro-1,3,5-triazine, 2-ethylamino- 4-tert-butylamino-6-chloro-1,3,5-triazine, 2,4-bis-isopropylamino-6-chloro-1,3,5-triazine, 2-isopropylamino-4- (3-methoxypropylamino) - 6-chloro-1,3,5-triazine, 2,4-bis-diethylamino-6-chloro-1,3,5-triazine, 2-ethylamino-4-diethylamino-6-chloro-1,3,5-triazine, or 2-ethylamino-4-sec-butylamino-6-chloro-1,3,5-triazine. Also to be emphasized are those chlorotriazines which contain only secondary amino groups as substituents, such as, for example, 2,4-bis-ethylamino-6-chloro-1,3,5-triazine, 2-ethylamino-4-isopropylamino-6-chloro 1,3,5-triazine, 2-ethylamino-4- (1-cyano-1-methylethylamino) -6-chloro-1,3,5-triazine, 2-ethylamino-4-tert-butylamino-6-chloro 1,3,5-triazine and 2-cyclopropylamino-4-isopropylamino-6-chloro-1,3,5-triazine.
Water-soluble salts of N-phosphonomethylglycine are, for example, the alkali metal salts such as the lithium, sodium or potassium salt, trialkylsulfonium salts such as the trimethylsulfonium salt and the ammonium salts.
Examples of amines suitable for salt formation are primary, secondary and tertiary aliphatic amines such as methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-pentylamine, iso-pentylamine, methylethylamine, Methylisopropylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, ethanolamine, n-propanolamine, isopropanolamine and diethanolamine.
Preferred water-soluble salts of N-phosphonomethylglycine are the monoalkylammonium salts or dialkylammonium salts, with a carbon chain length of 1 to 14 carbon atoms. The salts of N-phosphonomethylglycine with ethyl-, propyl-, dimethyl- or diethylamine, but especially isopropylamine, are very particularly preferred.
The isopropylammonium salt of N-phosphonomethylglycine is preferably used as the active ingredient of the formula I. Corresponding active ingredient suspensions according to the invention preferably contain on the one hand the isopropylammonium salt of N-phosphonomethylglycine and on the other hand a chlorotriazine of the formula II in which R¹ is chlorine.
Since the active compound concentrates according to the invention frequently have to be stored at temperatures which promote the growth of decomposing microorganisms, it is advisable to add an effective amount of a preservative to the agents ready for sale. In general, small amounts of 37% formaldehyde solution or 1,2-benzisothiazol-3-one serve this purpose. Usual concentrations of preservatives are between 0 and 0.5% by weight, in particular between 0.05 and 0.2% by weight. Since foaming on the diluted spray liquors is undesirable - the dosing accuracy is reduced, the distribution of active ingredients becomes inhomogeneous - antifoam agents are added to the concentrates. Silicone oils have proven to be particularly suitable. In their preferred embodiments, the suspensions according to the invention contain up to 10% by weight of foam-inhibiting silicone oils. The proportion of foam-inhibiting substances is preferably between 0.01 and 5% by weight, in particular between 0.05 and 2% by weight. To set an optimal degree of viscosity, it is often necessary to add a thickener that is water-soluble or swellable in water to the herbicidal suspension. Such suitable thickeners are: polysaccharides of the xantham type, alginate type, guar type, cellulose type or synthetic markromolecules such as polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, polyacrylates or swellable, structure-forming silicates such as pyrogenic or precipitated silicas, bentonite, hectorite, montmorillonite Attapulgite or organic derivatives of the above structures of aluminum silicates. Polysaccharides are preferred. Suspensions according to the invention contain up to 10 percent by weight of thickeners. The proportion is preferably between 0.01 and 5% by weight, but in particular between 0.05 and 0.2% by weight. In order to maintain the flowability of the herbicidal composition even at low temperatures and to prevent the aqueous homogeneous phase from freezing out, antifreeze agents are usually added to the agents according to the invention. Usual additives such as ethylene glycol, propylene glycol, glycerin, di-, tri- and tetraethylene glycol and urea are suitable for this. Up to 25% by weight of antifreeze can be added to the agents according to the invention. However, salable agents preferably contain no more than 10% by weight of antifreeze. Ethylene glycol or propylene glycol are preferably added as antifreeze. The amount of antifreeze used in practice depends on the geographic, climatic and seasonal conditions of the intended herbicide use.
The active ingredient suspensions according to the invention are suitable for the selective control of weeds in perennial crops. Such cultures mostly consist of trees. In particular, weeds are combated in these crops which can compete with the crop plants when ingesting food, water and light. So on the one hand only the weeds in the immediate vicinity of the plants, for example on the tree slices, but on the other hand also the weeds in the entire tree plantations can be pushed back. Examples of target cultures of the agents according to the invention are tropical and subtropical cultures such as coffee, rubber, cocoa, date palms, oil palms, coconut palms, bananas or citrus, but also cultures from temperate climates such as fruit (apples, pears, peaches, apricots, cherries, plums) Wine, nuts, avocados and olives. Planting of timber such as pine, fir, spruce or poplar can also be considered.
In preferred active ingredient suspensions according to the invention, in addition to the active ingredient components of the formulas I and II and the surfactant combination of the anionic surfactant of the formulas III, IV or V and the cationic surfactant of the formula VI, 0.01 to 5% of a water-soluble or water-swellable thickener, 01 to 5% of an anti-foaming agent and 0 to 25% of an antifreeze incorporated.
Among the anionic alternative surfactants of the formulas III, IV and V, the surfactants of the formula III have proven to be particularly suitable.
The compositions according to the invention are notable for excellent tolerance to biological or technical changes in the active ingredient content of the compositions. In a wide range, the surfactant component does not need to be varied, or only to a small extent, when the proportion of a herbicidal active ingredient is increased or decreased. No decomposition or coagulation of the suspension is observed even when the ready-to-sell suspension concentrates are stored for a long time. Slight settling of the solid disperse phase is only observed after very long storage. This settling process is normal and can be reversed by simply shaking or stirring. The suspension is therefore stable.
It is an advantage for the manufacturer that when a liquid water-soluble and a solid active ingredient are combined, the solid component can be suspended directly in a solution of the liquid component.
Preferred compositions according to the invention contain the following constituents: 10 to 25% by weight isopropylammonium salt of N-phosphonomethylglycine, 25 to 45% by weight of a triazine of the formula II, 0.3 to 5% by weight of an anionic surfactant of the formulas III, IV or V, 0.3 to 5% by weight of a cationic surfactant of the formula VI and ad 100% water by weight.
Contain further preferred active ingredient suspensions 13 to 25% by weight isopropylammonium salt of N-phosphonomethylglycine, 20 to 35% by weight of a triazine of the formula II, 0.3 to 3% by weight of an anionic surfactant of the formulas III, IV or V, 0.3 to 3% by weight of a cationic surfactant of the formula VI and ad 100% water by weight.
Of the above formulations, those which have a compound of the formula III as the anionic surfactant have particularly advantageous properties. The use of a surfactant of the formula III is particularly advantageous when formulating a chlorotriazine of the formula II. The suitability of this group of surfactants is particularly evident in the formulation of the chlorotriazine 2-ethylamino-4-tert.butylamino-6-chloro-1,3,5-triazine (terbutylazine). The preferred salable agents additionally contain 0.05 to 0.2% by weight of a water-soluble or water-swellable thickener, 0.05 to 2% by weight of an anti-foaming agent, 0.05 to 0.2% by weight of a preservative and 0 up to 10% by weight of an antifreeze.
Polysaccharide is used as the thickening agent, silicone oil as the antifoaming agent, formaldehyde or 1,2-benzisothiazol-3-one as the preservative and ethylene glycol or propylene glycol as the antifreeze.
Among the anionic surfactants of the formula III, preference is given to using those compounds for the preparation of the suspensions according to the invention in which X and Y are each for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> independently for numbers from 4 to 11 and <u style="single">r</u> represent a number from 1 to 3, and in particular in which <u style="single">m</u> and <u style="single">n</u> the number 6 and <u style="single">r</u> the number 2 mean.
Among the anionic surfactants of the formula IV, preference is given to using either those compounds for the formulation of the herbicidal active compounds in which R¹⁰ is hydrogen or styryl, A<sup>⊕</sup> for a triethanolammonium cation, <u style="single">s</u> for a number from 1 to 3 and <u style="single">t</u> represent a number from 10 to 30, in particular a mixture of mono- and di- (tristyrylphenol-octadecaglycol ether) -phosphoric acid ester-triethanol-ammonium salts; or those in which R¹⁰ is C₃-C₁₅ alkyl, A<sup>⊕</sup> for an alkali metal cation, <u style="single">s</u> for the number one and <u style="single">t</u> stand for a number from 5 to 13, in particular a mixture of mono- and di- (nonylphenol-nonaglycol ether) -phosphoric acid potassium salts.
Among the anionic surfactants of the formula V, those compounds are preferably used for the preparation of the active ingredient suspensions according to the invention in which B<sup>⊕</sup> stand for the triethanolammonium cation and R¹¹ for C₉-C₁₅-alkyl.
The cationic surfactant of formula VI is represented in the preferred embodiment of the present invention by compounds in which E<sup>⊖</sup> represent a halogen anion, R¹⁶, R¹⁷ and R¹⁸ represent methyl and R¹⁹ represent C₉-C₁₅-alkyl. In particular, the cationic surfactant of the formula VI is preferably dodecyltrimethylammonium chloride.
Very particularly preferred embodiments of the agents according to the invention contain 13 to 25% by weight isopropylammonium salt of N-phosphonomethylglycine, 20 to 35% by weight 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 0. 3 to 3% by weight of an anionic surfactant, of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, or a mono- and di- (tristyrylphenol-octadecaglycol ether) -phosphoric acid ester-triethanolammonium salt mixture, or a mono- and di- (nonylphenol-nonaglycol ether) -phosphoric acid ester-potassium salt mixture, or dodecylbenzenesulfononylsulfononylsulfononium sulfononium sulfononium sulfononium sulfonic acid trolane , 3 to 3% by weight of dodecyltrimethylammonium chloride, 0.05 to 0.2% by weight of polysaccharide, 0.05 to 2.0% by weight of silicone oil, 0.05 to 0.2% by weight 1,2-benzisothiazol-3-one or a 37% formaldehyde solution, 0 to 10% by weight ethylene glycol or propylene glycol, and ad 100% by weight water.
Specific preferred flowable, herbicidal active ingredient suspensions contain the following components:<ul id="ul0001" list-style="none"><li>1) 21% by weight isopropylammonium salt of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.5% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 1.5% by weight silicone oil, 0.13% by weight polysaccharide, 0.13% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>2) 14.5% by weight isopropylammonium salt of N-phosphonomethylglycine, 30% by weight 2-ethylamino-4-tert.butylamino-6-chloro-1,3,5-triazine, 1.6% by weight anionic surfactant of the formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 0.8% by weight silicone oil, 0.1% by weight polysaccharide, 0.1% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>3) 18% by weight isopropylammonium salt of N-phosphonomethylglycine, 31% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.6% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 0.8% by weight silicone oil, 0.1% by weight polysaccharide, 0.1% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>4) 21% by weight isopropylammonium salt of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 2% by weight of mono- and di- (tristyrylphenol octadecaglycol ether) phosphoric acid ester-triethanolammonium salt mixture, 0.75% by weight of dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.10% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>5) 21% by weight isopropylammonium salt of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 2% by weight of mono- and di- (nonylphenol-nonaglycol ether) -phosphoric acid-potassium salt mixtures, 0.75% by weight of dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.10% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>6) 21% by weight isopropylammonium salt of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 0.75% by weight dodecylbenzenesulfonic acid triethanolammonium salt, 0.9% by weight dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.1% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>7) 21% by weight isopropylammonium salt of N-phosphonomethylglycine, 26% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.5% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 1.4% by weight silicone oil, 0.15% by weight polysaccharide, 0.15% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>8) 15.6% by weight of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.5% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 1.5% by weight silicone oil, 0.13% by weight polysaccharide, 0.13% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>9) 10.7% by weight of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.6% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 0.8% by weight silicone oil, 0.1% by weight polysaccharide, 0.1% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>10) 13.3% by weight of N-phosphonomethylglycine, 31% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.6% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 0.8% by weight silicone oil, 0.1% by weight polysaccharide, 0.1% by weight 37% formaldehyde solution and ad 100% water by weight.</li><li>11) 15.6% by weight of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 2% by weight of mono- and di- (tristyrylphenol octadecaglycol ether) phosphoric acid ester-triethanolammonium salt mixture 0.75% by weight of dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.10% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>12) 15.6% by weight of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 2% by weight of mono- and di- (nonylphenol-nonaglycol ether) -phosphoric acid-potassium salt mixture 0.75% by weight of dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.10% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>13) 15.6% by weight of N-phosphonomethylglycine, 30% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 0.75% by weight dodecylbenzenesulfonic acid triethanolammonium salt, 0.9% by weight dodecyltrimethylammonium chloride, 0.1% by weight silicone oil, 0.15% by weight polysaccharide, 0.1% by weight 1,2-benzisothiazol-3-one and ad 100% water by weight.</li><li>14) 15.6% by weight of N-phosphonomethylglycine, 26% by weight of 2-ethylamino-4-tert-butylamino-6-chloro-1,3,5-triazine, 1.5% by weight of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight dodecyltrimethylammonium chloride, 1.4% by weight silicone oil, 0.15% by weight polysaccharide, 0.15% by weight 37% formaldehyde solution and ad 100% water by weight.</li></ul>
The active ingredient suspensions according to the invention have a density of 1.12 to 1.16 g / ml and a pH between 4.0 and 6.0. The viscosity is adjusted between 400 and 900 mPas with a suitable amount of thickener.
To prepare the suspension concentrates according to the invention, the entire active ingredient mixture is stirred, for example, in an aqueous solution or a suspension of the formulation auxiliaries, the coarse suspension obtained is comminuted, if appropriate, by pre-grinding in a suitable mill to finenesses of at most 200 μm and the product is then ground in attritor mills, tooth mills, colloid mills , Dyno mills or sand mills, until the particles of the suspension are present in particle sizes of 0.1 to 12 µm, preferably less than 5 µm. In particular, at least 50% of the particles have a diameter of less than 2.5 μm. The desired degree of viscosity (preferably 400-900 mPas) is set by adding a suitable amount of thickener.
The agents according to the invention are applied in a simple manner by diluting the suspension concentrates with the desired amount of water, stirring briefly and applying them to the plants. The spray liquors obtained from the suspension concentrates according to the invention are distinguished in particular by the uniform distribution of the active ingredient.
The invention is illustrated, but not limited, by the example below.
Example 1: Preparation of 100 l active ingredient suspension (114 kg)
26.7 kg of water are placed in a stirred vessel; 1.7 kg of anionic surfactant of formula III, wherein X and Y for ethylene bridges, Z for R⁶, M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2; 1.7 kg of 35% dodecyltrimethylammonium chloride solution, 1.7 kg of silicone oil and 39.2 kg of a 62% solution of the isopropylammonium salt of N-phosphonomethylglycine are stirred together until homogeneous. 35.5 kg of 97% 2-ethylamino-4-tert.butylamino-6-chloro-1,3,5-triazine are added to this mixture and the mixture is ground first in a toothed colloid mill and then in a ball mill to a particle size less than 12 µm, with 50% of the solid particles being smaller than 2.2 µm. A gel of 0.15 kg of polysaccharide (xantham gum), 7.2 kg of water and 0.15 kg of 37% formaldehyde solution which has been pre-swollen for at least 4 hours is added to this ground suspension. This gives 100 l of active ingredient suspension with a viscosity of 500-800 mPas, a density of 1.14 ± 0.015 g / ml and a pH between 4.0 and 6.0, containing 21% by weight of isopropylammonium salt of N-phosphonomethylglycine , 30% by weight of 2-ethylamino-4-tert.butylamino-6-chloro-1,3,5-triazine, 1.5% by weight of anionic surfactant of the formula III, where X and Y for ethylene bridges, Z for R⁶ , M<sup>⊕</sup> for a sodium cation, <u style="single">m</u> and <u style="single">n</u> for the number 6 and <u style="single">r</u> stand for the number 2, 0.5% by weight of dodecyltrimethylammonium chloride, 1.5% by weight of silicone oil, 0.13% by weight of polysaccharide, 0.13% by weight of 37% formaldehyde solution and ad 100% by weight of water.
The other embodiments 2) to 14) of the present invention specifically mentioned above are obtained in an analogous manner.
40 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40
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12 members in 8 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 321588 | Switzerland | – | |
| 321588 | Switzerland | A | |
| 321588 | Switzerland | A | |
| 321588 | – | – | – |
| CH19880003215 | – | – | – |
Members12
| Document | Office | Kind | |
|---|---|---|---|
| FI894020A0 | Finland | A0 | |
| NO893456D0 | Norway | D0 | |
| FI894020A | Finland | A | |
| NO893456L | Norway | L | |
| EP0357553A2This record | European Patent Office (EPO) | A2 | |
| AU4089389A | Australia | A | |
| KR900002705A | Republic of Korea | A | |
| JPH02111707A | Japan | A | |
| ZA896593B | South Africa | B | |
| EP0357553A3 | European Patent Office (EPO) | A3 | |
| JPH062647B2 | Japan | B2 | |
| MY104176A | Malaysia | A |
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Numbers
- Publication
- 0357553
- Publication, DOCDB
- 0357553
- Publication, EPODOC
- EP0357553
- Application
- 89810622
- Application, DOCDB
- 89810622
- Application, EPODOC
- EP19890810622
Titles3
- German
- Herbizide Mischungen
- English
- Herbicidal mixtures
- French
- Mélanges herbicides
Classification
- CPC, 2
- A01N57/20
- A01N43/66
- IPC, 3
- A01N25 04
- A01N25 30
- A01N57 20
Designated states1
- Contracting states, 1
- Sweden