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WO1997000010A1 - Tensioactifs ameliorant l'efficacite et/ou la resistance a l'entrainement par la pluie de formulations de pesticides - Google Patents

Tensioactifs ameliorant l'efficacite et/ou la resistance a l'entrainement par la pluie de formulations de pesticides Download PDF

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Publication number
WO1997000010A1
WO1997000010A1 PCT/US1996/010467 US9610467W WO9700010A1 WO 1997000010 A1 WO1997000010 A1 WO 1997000010A1 US 9610467 W US9610467 W US 9610467W WO 9700010 A1 WO9700010 A1 WO 9700010A1
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WIPO (PCT)
Prior art keywords
composition
glyphosate
surfactant
alcohol
surfactants
Prior art date
Application number
PCT/US1996/010467
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English (en)
Inventor
James M. Warner
Original Assignee
Monsanto Company
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 Monsanto Company filed Critical Monsanto Company
Priority to JP50340097A priority Critical patent/JP3980640B2/ja
Priority to AU63863/96A priority patent/AU696607B2/en
Priority to EP96923316A priority patent/EP0854676A4/fr
Priority to NZ312352A priority patent/NZ312352A/xx
Publication of WO1997000010A1 publication Critical patent/WO1997000010A1/fr

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    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • This invention comprises a new method of use of relatively low-cost, agriculturally acceptable surfactants to enhance the efficacy or rainfastness of foliar-applied pesticidal and plant growth modifying agents.
  • This invention further comprises new and useful compositions of such agents, in particular the herbicide N-phosphonomethylglycine or its salts or mixtures thereof, containing such efficacy- or rainfastness-enhancing surfactants.
  • Foliar-applied pesticidal and plant growth modifying chemicals are widely used in agricultural, industrial, recreational and residential areas worldwide. These chemical agents illustratively include insecticides, fungicides, herbicides, plant growth regulators and plant nutrients among other chemicals. Such chemicals are typically applied by spraying on the foliage of vegetation to be protected, controlled, killed or modified, but other methods such as rope-wick application are known. Some of these agents show contact action, killing, controlling or modifying the growth of target organisms at the site of deposition. Other chemicals are systemic, translocating within the plant to a site of action remote from the site of deposition. Still other chemicals show both contact and systemic action.
  • Methods to enhance rainfastness include addition to the spray solution of oils or other lipophilic substances, polymers and other materials which are alleged to enhance spreading and sticking ofthe applied formulation to leaves, and addition of various surfactants.
  • surfactants which have been disclosed for rainfastness enhancement are organosilicone copolymers, for example the ethoxylated siloxane Silwet L-77 of Union Carbide Corporation.
  • Such surfactants, as well as other spray additives used to enhance rainfastness tend to be relatively expensive and many have other drawbacks.
  • a rainfastness enhancing material may be provided by the manufacturer or supplier ofthe foliar-applied pesticidal or plant growth modifying agent as an ingredient in the formulation of said agent.
  • N-phosphono-methylglycine also known by its common name glyphosate.
  • Glyphosate is a highly effective and commercially important herbicide useful for combating the presence of a wide variety of unwanted vegetation, including agricultural weeds. Glyphosate is applied as a formulated product to the foliage of annual and perennial grasses and broadleaf plants and the like, and is taken up over a period of time into the leave whence it translocates throughout the plant.
  • Glyphosate in ionic form has relatively high water solubility, especially when formulated as a salt, and during the uptake period immediately after application glyphosate is vulnerable to being washed off the foliage by rain or by overhead watering or irrigation. As glyphosate has practically no herbicidal activity in the soil, its efficacy is seriously reduced by such washing.
  • the length of time during which glyphosate is somewhat vulnerable to rain depends on many environmental and plant factors, and on the duration and intensity of rain, but can be as short as thirty minutes or as long as twelve hours or more after application. In the great majority of cases rain falling six or more hours after application does not seriously affect performance ofthe herbicide.
  • glyphosate is formulated in commercial compositions in the form of a water-soluble salt.
  • Salts in commercial use include alkylamine salts, such as the isopropylamine salt, alkali metal salts, such as the sodium salt, the ammonium salt and the trimethylsulfonium salt.
  • formulations of glyphosate in its acid form are also used.
  • Typical glyphosate salt formulations include aqueous concentrates, requiring simple dilution in water for application by the end-user, and water-soluble or water-dispersible dry formulations, especially granules, requiring dissolution or dispersion in water prior to application.
  • Most formulations, whether liquid or dry also contain one or more surfactants.
  • siloxane surfactant Silwet L-77 has been the subject of much published research into rainfastness enhancement for glyphosate salt formulations. Its main active ingredient is 1,1,1,3,5,5,5-heptamethyltrisiloxanylpropyl- omega-methoxypoly (ethylene oxide) where the average number of ethylene oxide units is approximately seven. Other siloxanes of related composition are also described in the art.
  • acetylenic diol surfactants are obtainable at much lower cost than effective organosilicone surfactants, they could still be too costly for many applications.
  • the end-user wishes some degree of insurance against the possibility of rain washing the herbicide off the foliage before it has had time to penetrate into the leaves. The end- user seldom knows that it will certainly rain. For such insurance purposes, economics dictate a still lower-cost adjuvant or formulation ingredient.
  • Various low-cost surfactants have from time to time been claimed to give rainfastness enhancement, including ethoxylated alkylphenols such as octylphenol and nonylphenol ethoxylates.
  • compositions comprising glyphosate or one or more of its salts, an alcohol alkoxylate surfactant of molecular structure defined below and one or more other surfactants, said compositions showing enhanced rainfastness by comparison with similar compositions not containing said alcohol alkoxylate surfactant, and showing at least equal rainfastness by comparison with much higher-cost compositions ofthe prior art based on ethoxylated siloxane or acetylenic diol surfactants.
  • Not all alcohol alkoxylate surfactants provide the desired degree of rainfastness enhancement.
  • Alcohol alkoxylates of molecular structure defined below when used in accordance with the present invention, give superior rainfastness by comparison with, for example, primary linear alcohol alkoxylates or alkylphenol alkoxylates ofthe prior art.
  • compositions comprising glyphosate or one or more of its salts, an alcohol alkoxylate surfactant of molecular structure defined below and one or more other surfactants, said compositions showing enhanced herbicidal efficacy by comparison with glyphosate compositions known in the art, whether rain occurs shortly after application or not.
  • surfactants used in combination with alcohol alkoxylates in compositions ofthe present invention are ethoxylated tertiary and quaternary alkylamines and alkylamine oxides.
  • ethoxylated alkylamine or alkylamine oxide surfactants having an average alkyl chain length in the range from 10 to 20 carbon atoms and having an average of from 2 to 20 moles of ethylene oxide (EO) per mole of amine, are effective in potentiating the herbicidal activity of glyphosate compositions.
  • European Patent No. 0 290416 discloses glyphosate compositions containing tertiary alkylamine surfactants within the range encompassed by the above description, and notes that such compositions, particularly those with EO levels in the lower part ofthe range mentioned above, have high herbicidal unit activity.
  • 0274369 discloses highly efficacious glyphosate compositions containing quaternary alkylamine surfactants within the range encompassed by the above description. In both cases it is disclosed that for best performance the compositions should also contain a significant amount of an inorganic ammonium salt such as ammomum sulfate.
  • US Patent No. 5,118,444 discloses ethoxylated alkylamine oxide surfactants within the range encompassed by the above description, and indicates their usefulness as components of glyphosate formulations.
  • Ammonium sulfate is bulky and can only be accommodated in a concentrate formulation at an effective level by greatly lowering the content of active ingredient, in this case glyphosate.
  • a significant advance in the art of formulating glyphosate concentrates would result from identification of a material which further enhances the efficacy of compositions containing ethoxylated alkylamine surfactants, but which is effective at a lower concentration than is required in the case of ammonium sulfate. That material could be incorporated in a concentrate formulation without unacceptable dilution ofthe glyphosate active ingredient.
  • the present invention provides just such an advance in the art.
  • Ri and R 2 are independently straight or branched chain Ci to about C 2 s alkyl, aryl or alkylaryl groups and the total number of carbon atoms in Ri and R 2 is about 7 to about 30, R 3 is hydrogen, R, groups are independently Ci to C 4 alkylene groups, m is a positive integer from 1 to 3 and n is an average number from about 3 to about 30.
  • glyphosate or one of its agriculturally acceptable salts comprising (a) glyphosate or one of its agriculturally acceptable salts, (b) one or more alcohol surfactants such as those having the representative chemical structure.
  • Ri and R 2 are independently straight or branched chain Ci to about C 2 8 alkyl, aryl or alkylaryl groups and the total number of carbon atoms in Ri and R 2 is about 7 to about 30, R 3 is hydrogen, Ri groups are independently Ci to C 4 alkylene groups, m is a positive integer from 1 to 3 and n is an average number from about 3 to about 30, and (c) one or more other surfactants.
  • R 3 in the structure ofthe alcohol surfactant is hydrogen and R 4 is ethylene.
  • compositions ofthe invention possess at least one ofthe following benefits over compositions known in the art. (1) They may show enhanced rainfastness by comparison with similar compositions not containing said alcohol surfactants, and at least substantially equal rainfastness by comparison with much higher-cost compositions ofthe prior art based on ethoxylated siloxane or acetylenic diol surfactants. (2) They may show enhanced herbicidal efficacy, even in the absence of rain, by comparison with similar compositions not containing said alcohol surfactants.
  • a method of use of such compositions to provide acceptable control of weeds and other unwanted vegetation whether or not rain falls shortly after application is also provided.
  • the herbicide glyphosate is formulated as its isopropylamine salt. Excellent control of most plant species can normally be obtained at rates of 0J to 10 kg/ha of glyphosate-isopropylamine. It is generally preferred to refer to the amount of glyphosate applied in terms of glyphosate acid equivalent, conventionally abbreviated as "a.e.' ⁇ Application to plants is most commonly done by spraying a solution ofthe glyphosate herbicide in water.
  • the efficacy of glyphosate is significantly improved by the presence of a surfactant.
  • surfactants are equally effective in improving the herbicidal activity of glyphosate, and some surfactants are quite ineffective or may even reduce glyphosate activity.
  • alkoxylated alkylamine surfactants including both tertiary and quaternary amine types.
  • Nonionic surfactants differ widely and to a large extent unpredictably in their ability to enhance glyphosate activity.
  • the alcohol alkoxylates ofthe present invention are relatively weak in this regard, when used as the sole surfactant.
  • glyphosate salt formulations already contain one or more surfactants, most commonly ofthe tertiary or quaternary alkylamine alkoxylate class mentioned above.
  • Roundup® herbicide of Monsanto Company is an aqueous concentrate formulation ofthe isopropylamine salt of glyphosate.
  • Roundup herbicide as sold, for example, in Canada contains a surfactant based on ethoxylated tallowamine having an average of about 15 moles EO per mole of amine.
  • the end-user may add more surfactant to a glyphosate spray solution; as well as amines, low-cost nonionic surfactants ofthe ethoxylated primary linear alcohol, alkylphenol or fatty acid classes are especially widely used in this way.
  • amines low-cost nonionic surfactants ofthe ethoxylated primary linear alcohol, alkylphenol or fatty acid classes are especially widely used in this way.
  • an effective surfactant in the concentrate formulation.
  • these alcohol surfactants suffer the further drawback that they cannot be formulated with glyphosate salts in agriculturally useful amounts in aqueous concentrates, except in the presence of compatibilizing agents.
  • Such agents include a wide variety of tertiary and quaternary amine surfactants, alkyl polyglycosides and other materials.
  • Ri and R 2 are independently straight or branched chain Ci to about C 2 * alkyl, aryl or alkylaryl groups and the total number of carbon atoms in R x and R 2 is about 7 to about 30, R 3 is hydrogen, 4 groups are independently Ci to C 4 alkylene groups, m is positive integer from 1 to 3 and n is an average number from about 3 to about 30, preferably from about 7 to about 14, and most preferably from about 9 to about 12.
  • Ri and R 2 are preferably straight-chain alkyl groups with a total of about 10 to about 20 carbon atoms, R 3 is preferably hydrogen, R» is preferably ethylene and m is preferably 1.
  • Ri and R 2 are independently straight or branched chain Ci to about C 28 alkyl, aryl or alkylaryl groups and the total number of carbon atoms in Ri and R 2 is about 7 to about 30, R 3 is hydrogen, R groups are independently Ci to C alkylene groups, m is positive integer from 1 to 3 and n is an average number from about 3 to about 30, and (c) one or more other surfactants, said compositions showing enhanced efficacy and/or rainfastness by comparison with similar compositions not containing said alcohol surfactants, and showing at least substantially equal rainfastness by comparison with much higher-cost compositions ofthe prior art based on ethoxylated siloxane or acetylenic diol surfactants.
  • a method of use of such compositions to provide acceptable control of weeds and other unwanted vegetation whether or not rain falls shortly after application is also provided.
  • a particular embodiment of this invention is a surfactant composition
  • a surfactant composition comprising (a) an alcohol surfactant in which R 3 is hydrogen, Ri and R 2 are straight chain alkyl groups with a total of about 10 to about 20 carbon atoms, R is ethylene, m is 1 and n is an average number in the range from about 7 to about 14, most preferably from about 9 to about 12; and (b) an ethoxylated tertiary or quaternary alkylamine or alkylamine oxide surfactant having an average of from about 2 to about 20 moles of ethylene oxide per mole of amine.
  • Said surfactant composition may be coformulated with a glyphosate herbicide in an aqueous or dry concentrate formulation. Alternatively, said surfactant composition may be provided to the end user separately from the glyphosate herbicide, for tank mixing by him immediately prior to application.
  • the ethoxylated alcohol group can be located anywhere on the alkyl chain except at the ends, and such preparations are therefore mixtures of alcohols.
  • the alkyl chain length also normally varies within commercial preparations.
  • C ⁇ -u secondary alcohol 9 EO This product has a total of about 11 to about 15 carbon atoms in the alkyl chain and an average of about 9 moles ethylene oxide per mole of alcohol
  • Ri and R 2 are straight chain alkyl groups with a total of about 10 to about 20 carbon atoms, R 3 is hydrogen, R» is ethylene, m is 1 and n is an average number in the range from about 7 to about 14.
  • Such surfactants may be produced by reacting ethylene oxide, according to methods known in the art, with alcohols known in the art as "Guerbet alcohols".
  • alcohol alkoxylates ofthe invention may be used at concentrations in the spray solution in the range from about 0.05 to about 2 per cent by volume, preferably from about 0.1 to about 1 per cent by volume, although in certain circumstances greater or lesser concentrations may be used.
  • the alcohol alkoxylate surfactant may usefully be included at weight/weight ratios of said surfactant to glyphosate a.e. from about 1:20 to about 1:1, preferably from about 1:12 to about 1:2 and most preferably from about 1:6 to about 1:3.
  • glyphosate is typically present at about 0.5 to about 2 per cent a.e. by weight.
  • Aqueous concentrate formulations ofthe invention may contain about 5 to about 40 per cent glyphosate a.e. by weight.
  • Dry concentrate formulations ofthe invention may contain about 10 to about 75 per cent glyphosate a.e. by weight.
  • Preferred dry concentrate formulations are water- soluble granules containing about 40 to about 70 per cent glyphosate a.e. by weight.
  • Preferred glyphosate salts for use in aqueous or dry formulations ofthe invention include ammonium, alkylamine, for example isopropylamine, alkylsulfonium, for example trimethylsulfonium, and alkali metal salts. Most commonly these salts have a molar ratio of actions to glyphosate anions in the range from about 1:1 to about 2:1.
  • alcohol alkoxylates are incorporated at useful levels in an aqueous concentrate formulation of glyphosate salt by further including in the formulation a compatibilizing agent which raises the cloud point ofthe formulation to an acceptable level, for example 50 ' C or higher.
  • a compatibilizing agent which raises the cloud point ofthe formulation to an acceptable level, for example 50 ' C or higher.
  • additional surfactant(s) should be included in an amount sufficient to provide acceptable herbicidal efficacy in the absence of rain, and to allow the alcohol alkoxylate to exhibit the desired level of rainfastness enhancement.
  • the amount of such additional surfactant other than alcohol alkoxylate to be included depends greatly on the chemical composition of that surfactant, on the plant species targeted and on environmental factors. Normally, however, the weight/weight ratio of alcohol alkoxylate to the total of other surfactants is in the range from about 1:20 to about 5:1, preferably from about 1:10 to about 2:1 and most preferably from about 1:5 to about IJ.
  • the surfactant(s) additional to alcohol alkoxylates in glyphosate compositions of the invention may be selected from alkyl monoglycosides, alkyl polyglycosides, sucrose alkylesters, secondary, tertiary, or quatemary alkylamine alkoxylates, non-alkoxylated tertiary or quaternary alkylamines, alkylamine oxides, alkylbetaines and the like. Good results may be obtained, for example, with cocoamine 2 EO and 5 EO (e.g.
  • N-methyltallowammonium chloride 5 EO, 10 EO and 15 EO N-methyloctadecylammonium chloride 15 EO (e.g. Ethoquad 18/25, Akzo Chemicals Inc.).
  • N-methylcocoammonium chloride 2 EO formulated at 35% concentration in water as Ethoquad C/12W, Akzo Chemicals Inc.
  • N- methylcocoammonium chloride 15 EO e.g.
  • Ethoquad C/25, Akzo Chemicals Inc. N, N- diethyl-N-methylammonium chloride 1 EO + 7PO (Emcol CC-9, Witco Corporation), N, N-dimethyldodecylamine (Armeen DM12D, Akzo Chemicals Inc.), N,N,N- trimethylcocoammonium chloride (formulated at 33% concentration in water as Arquad C-33W, Akzo Chemicals Inc.), N,N,N-trimethyltallowammonium chloride (formulated at 27% concentration in water as Arquad T-27W, Akzo Chemicals Inc.), potassium laurylbetaine, alkyl polyglucosides (Agrimul PG 2067 and Agrimul PG 2069, Henkel Corporation), Cs-io alkyl monoglucoside, and sucrose cocoate (Crodesta SL-40, Croda Inc.).
  • glyphosate with other herbicides are also within the scope ofthe present invention.
  • other herbicides include bialaphos, glufosinate, 2,4-D, MCPA, dicamba, diphenylethers, imidazolinones and sulfonylureas.
  • Aqueous concentrate formulations ofthe invention are diluted in an appropriate volume of water and applied, for example by spraying, to the weeds or other unwanted vegetation to be killed or controlled.
  • Dry concentrate formulations ofthe invention are dissolved or dispersed in an appropriate volume of water and applied in the same way.
  • the present invention is illustrated by but not limited to the following Examples. In describing concentrate compositions ofthe Examples, percentages are given by weight unless otherwise indicated. In describing concentrations of surfactants in spray solutions, percentages are given by volume.
  • Comparative herbicidal activity with and without simulated rain was deterrnined in greenhouse and field tests.
  • seeds or propagules of selected species were planted in 10.2 cm square pots of soil with added fertilizer. Temperature and relative humidity were allowed to fluctuate within limits defined for each test described in the following Examples. Plants were allowed to grow until the desired growth stage or size (defined for each test) for spraying. Pots were selected for uniformity before treatment and three replicate pots were assigned to each treatment.
  • Spray solutions were prepared by dilution or dissolution of concentrate herbicide formulations in water. When desired to test "tank mix" application of surfactant compositions, these were added to other spray solution at the required concentration.
  • Spraying was performed with a device which simulates agricultural field spraying equipment, delivering a fine spray at a pressure of about 207 kilopascals. Speed of travel ofthe spray device over the plants was adjusted to give the desired spray volume (defined for each test). For logistical reasons, all three replicates of each treatment were sprayed together. "Rain” treatments were applied by repeated passage of a coarse spray of water over the plants at some desired period of time after herbicide spraying. The amount and duration of "rain” were noted. After spraying and "rain” treatment, the plants were returned to the greenhouse. Herbicidal efficacy was evaluated by visual assessment at one or more selected time periods after treatment and recorded as "percent control" on an arbitrary scale by comparison with untreated plants. On this scale 0 means no visible effect and 100 means death of all plants. In the Examples, percent control values given are the means of three replicates.
  • Adjuvant 3 + cocoamine quat 2 EO (1:1 ratio) In this and other Examples, a number followed by "EO” refers to the average moles of ethylene oxide per mole of surfactant.
  • Glyphosate was applied as the isopropylamine salt, either without surfactant (the glyphosate formulation sold as Accord® herbicide by Monsanto Company) or with a surfactant based on tallowamine ethoxylate (the glyphosate formulation sold as Roundup® herbicide by Monsanto Company).
  • Triton AG-98 (Union Carbide Corporation) is a widely used low foam commercial agricultural adjuvant, 80% of which is octylphenol ethoxylate.
  • E. Echinochloa crus-galli var. frumentae Japanese millet, ECHCF
  • Echinochloa crus-galli barnyardgrass, ECHCG
  • Table 1 show percent inhibition as recorded 15 days after treatment (DAT) with glyphosate at the rate of 0.25 lb. a.e./acre (0.28 kg a.e./ha), without and with "rain” described above.
  • DAT percent inhibition as recorded 15 days after treatment
  • the adjuvants were applied at a concentration of 0.25% in the spray solution.
  • adjuvant 4 was applied at 0.25%, but the other adjuvants were applied , through operator error, at 0.125%. This error does not affect any ofthe conclusions drawn below from this test.
  • Adjuvant 3 (containing a secondary alcohol ethoxylate) to provide significant rainfastness enhancement of Roundup. While not giving complete rainfastness under the severe conditions of this test, the use of Adjuvant 3 nevertheless gave greater enhancement of rainfastness than the Triton AG-98 (Adjuvant 1 ofthe prior art) and was at least as effective overall as 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol 10 EO (Adjuvant 2 ofthe prior art) which is a much higher-cost material.
  • Adjuvant 4 provided a similar degree of rainfastness enhancement to Adjuvant 3, and when added to the surfactantless product Accord gave similar performance with "rain” as when added to the surfactant-containing product Roundup.
  • Example 2
  • Aqueous concentrate formulations ofthe isopropylamine salt of glyphosate were prepared at a glyphosate a.e. loading of 18.4% (equivalent to about 200 g a.e./liter). All contained 7% cocoamine quat 2 EO and 10.2% nonionic surfactant.
  • the nonionic surfactant was selected from several secondary alcohol ethoxylates; Silwet L-77, 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol 10 EO, nonylphenol 8 EO, 10 EO and 12 EO and C12-15 primary alcohol 7 EO, 9 EO and 12 EO. These formulations were tested for rainfastness in a greenhouse test.
  • test species was Panicum maximum (guineagrass, PANMA). All glyphosate formulations were applied at 1.5 lb a.e./acre (1.68 kg a.e./ha) in a spray volume of 20 gallons/acre (185 l/ha). Commercial Roundup herbicide was included as a standard.
  • Aqueous concentrate formulations ofthe isopropylamine salt of glyphosate were prepared at a glyphosate a.e. loading of 31% (equivalent to about 360 g a.e./liter). All contained 7.5% cocoamine quat 2 EO and 8.6% nonionic surfactant. Formulations contained as the nonionic Cn-15 secondary alcohol 9 EO or C12 branched secondary alcohol 10 EO; for comparison, other formulations were made containing nonionic disclosed as rainfastness aids in the prior art such as 2, 4, 7, 9-tetramethyl-5-decyne-4, 7- diol 10 EO or nonylphenol 8 EO. These formulations were tested for rainfastness in a greenhouse test.
  • the test species was Elymus repens (quackgrass, AGRRE). All glyphosate formulations were applied at both 0.75 and 1.5 lb. a.e./acre (0.84 and 1.68 kg a.e./ha) in a spray volume of 20 gallons/acre (187 l/ha). Commercial Roundup herbicide was included as a standard. Simulated rain was apphed in the amount of 6 mm over a period of 15 minutes, beginning 1 hour after glyphosate treatment. Data on percent inhibition without and with "rain” are presented in Table 3. Table 3 : Percent inhibition of quackgrass 28 DAT without simulated rain (means of 3 replicates).
  • both formulations containing secondary alcohols gave better rainfastness than the formulation ofthe prior art containing 2, 4, 7, 9- tetramethyl-5-decyne-4, 7-diol 10 EO, and the formulation ofthe invention containing Cn-is secondary alcohol 9 EO gave better rainfastness than either ofthe prior art formulations.
  • both formulations ofthe present invention gave better rainfastness than the formulation ofthe prior art containing nonylphenol 8 EO, and gave comparable rainfastness to the much higher cost formulation containing 2, 4, 7, 9-tetramethyl-5-decyne-4,7diol 10 EO.
  • Cn-is secondary alcohol 9 EO and C12 branched secondary alcohol 10 EO ofthe present invention are more consistent in their rainfastness enhancing performance than nonylphenol ethoxylates ofthe prior art.
  • glyphosate formulations were tested for herbicidal activity and rainfastness by comparison with Roundup® herbicide in a field trial;
  • Formulation A 31% glyphosate a.e. as the isopropylamine salt, 7.5% cocoamine quat 2 EO, 8.6% nonylphenol 8 EO.
  • Formulation B 31% glyphosate a.e. as the isopropylamine salt, 7.5% cocamine quat 2 EO, 8.6% Cn-is secondary alcohol 9 EO.
  • a total of 7 grass and broadleaf species were planted in rows: L. Digitaria ciliaris (southern crabgrass, DIGSP) M. Brachiaria platyphylla (broadleaf signalgrass, BRAPP)
  • Sorghum halepense johnsongrass, SORHA
  • Echinochloa crus-galli barnyardgrass, ECHCG
  • Sida spinosa prickly sida, SIDSP
  • Echinochloa crus-galli var. frumentae Japanese millet, ECHCF
  • Sesbania exaltata hemp sesbania, SEBEX
  • Data in Table 4 show percent inhibition as recorded 21 days after treatment (DAT) with glyphosate at the rate of 0.75 lb. a.e./acre (0.84 kg a.e./ha), without and with "rain” as described above.
  • Examples 5-7 a short-term whole plant assay was used to evaluate relative efficacy of aqueous glyphosate compositions containing tallowamine 5 EO and either Cn. is secondary alcohol 9 EO or a Guerbet alcohol in different concentrations and proportions relative to one another.
  • pots were bottom watered at 1200 hr on the first day, resulting in rapid saturation ofthe growing medium. Seedling emergence occurred on the third and fourth days. On the seventh day, all pots were fertilized by bottom watering with a Peters 20-20-20 fertilizer containing 475 ppm soluble nitrogen. On the eighth day, pots were sorted into 6 replicate blocks according to plant size.
  • Treatments including no-treatment controls, were randomly assigned within each block, one treatment per pot.
  • Plants were treated with glyphosate compositions in rapid succession between 0830 hr and 0900 hr on the ninth day, when average plant height was 13-15 cm and the second leaf was just beginning to elongate.
  • Compositions were applied using a calibrated single-nozzle track sprayer delivering 187 l/ha through a Teejet 800 IE nozzle at 276 kilopascals. Plants were removed from the growth chamber immediately before treatment and returned to the same growth chamber immediately after treatment. Pots were spatially arranged in a randomized complete block experimental design. At 6 hours after treatment, plants in all pots were trimmed by cutting to 20 mm above the top edge ofthe pot. This removed approximately 90% ofthe barley leaf area. Pots were bottom watered once daily for the remainder ofthe study. Data collection took place on the sixteenth day, 7 days after treatment.
  • compositions in this Example contained glyphosate as the isopropylamine salt at a concentration calculated to deliver 0.42 kg a.e./ha.
  • Polyoxyethylene tallowamine 5 EO (T/Am 5) concentration was varied independently of Cn-is secondary alcohol 9 EO (S/Al 9) concentration as will be clear from the tables below.
  • Untreated plants had a mean regrowth height of 175 mm. Mean height of regrowth (mm)
  • Comparisons may be drawn between certain 1 : 1 combinations of S/Al 9 and T/Am 5 and either S/Al 9 alone or T/Am alone at the same total surfactant concentration as shown in the following table.
  • Aqueous formulations of glyphosate as the isoproplyamine salt containing T/Am, an ethoxylated Guerbet alcohol, and a 50/50 weight % blend of these surfactants were prepared.
  • Various such ethoxylated Guerbet alcohols have been included in formulations of this type, having the following representative chemical structure:
  • Gl in which x + y is 8 and n is an average of 7.7
  • G2 in which x + y is 12 and n is an average of 9.0.
  • the formulations of this example were combined with aqueous solution of isopropyl amine salt of glyphosate and the resulting solution was further diluted with water to produce a spray solution.
  • the spray solution was sprayed on plants in a greenhouse to determine their herbicidal efficacy.
  • compositions containing glyphosate with tallowamine, glyphosate with Guerbet alcohol surfactant, and glyphosate with a Guerbet alcohol surfactant/tallowamine blend were apphed at three different dosages to barley plants. The percentage inhibition was then recorded in terms of net inhibition of vertical growth (VG) and net inhibition of fresh weight (FW). The following results were obtained: tallowamine Guerbet blend
  • total surfactant 0.125% glyphosate 0.0625 lb/acre 9 8 4 -1 26 28 glyphosate 0J25 lb/acre 45 49 -1 5 35 42 glyphosate 0.25 lb/acre 65 63 25 26 61 55
  • total surfactant 0.25% glyphosate 0.0625 lb/acre 20 16 8 13 28 30 glyphosate 0J25 lb/acre 41 34 -5 7 58 53 glyphosate 0.25 lb/acre 60 61 18 20 69 64
  • total surfactant 0.0625% glyphosate 0.0625 lb/acre 12 12 -2 -5 24 27 glyphosate 0J25 lb/acre 37 35 7 16 54 50 glyphosate 0.25 lb/acre 54 53 28 29 65 53
  • total surfactant 0.0125% glyphosate 0.0625 lb/acre 17 19 4 -6 19 15 glyphosate 0J25 lb/acre 10 18 1 3 47 41 glyphosate 0.25 lb/acre 44 47 23 20 67 61
  • Velvetleaf and barnyardgrass were planted in standard 4 inch pots which contained a 50% mixture of Metro Mix and- 50% Dupo silt loam soil. This soil mix was previously steam sterilized and prefertilized with Osmocote (14-14-14) slow release fertilizer at a rate of 100 gm per cubic foot. Approximately one week after emergence any unhealthy or extra plants were removed to create a uniform test pot prior to herbicide apphcation. Herbicide apphcations were made via a track sprayer. The standard formulation used in this test was the commercial product Roundup® herbicide as sold in Canada, as described above. All pots were then placed in a warm supplemental lighted (approx. 475 microeinsteins) greenhouse and subirrigated to maintain adequate soil moisture for the duration ofthe test.
  • a series of concentrated formulations were prepared containing 24 percent glyphosate as the isopropylamine salt of glyphosate and a mixture of a Guerbet alcohol (G3) ofthe formula of Example 7 with T/Am5.
  • G3 of T/Am5 varied from about 2: 1 to about 8: 1.
  • the cloud point ofthe compositions were determiend to range from 57 degrees C to 86 degrees C.
  • the highest cloud points were obtained with the highest ratios of T/Am 5/G3 ratios.
  • all compositions were satisfactory with respect to practical utihty with respect to this aspect ofthe concentrate compositions.

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

Abstract

On ajoute des tensioactifs à base d'alcool, tel que de l'alcool de Guerbet éthoxylé, à une composition contenant d'autres tensioactifs, afin d'améliorer l'efficacité et/ou la résistance à l'entraînement par la pluie de compositions herbicides contenant du glyphosate ou ses sels. Ces compositions peuvent se présenter sous la forme de solutions concentrées stables à la conservation, diluées ou solubles dans l'eau, qu'on peut appliquer directement au feuillage.
PCT/US1996/010467 1995-06-16 1996-06-17 Tensioactifs ameliorant l'efficacite et/ou la resistance a l'entrainement par la pluie de formulations de pesticides WO1997000010A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP50340097A JP3980640B2 (ja) 1995-06-16 1996-06-17 農薬製剤の効力及び／又は耐雨性を増強する界面活性剤
AU63863/96A AU696607B2 (en) 1995-06-16 1996-06-17 Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations
EP96923316A EP0854676A4 (fr) 1995-06-16 1996-06-17 Tensioactifs ameliorant l'efficacite et/ou la resistance a l'entrainement par la pluie de formulations de pesticides
NZ312352A NZ312352A (en) 1995-06-16 1996-06-17 Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49146695A 1995-06-16 1995-06-16
US08/491,466 1995-06-16

Publications (1)

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WO1997000010A1 true WO1997000010A1 (fr) 1997-01-03

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EP (1) EP0854676A4 (fr)
JP (1) JP3980640B2 (fr)
AU (1) AU696607B2 (fr)
CA (1) CA2224364A1 (fr)
NZ (1) NZ312352A (fr)
WO (1) WO1997000010A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998035553A1 (fr) * 1997-02-14 1998-08-20 Imperial Chemical Industries Plc Compositions tensioactives agrochimiques
WO1999055155A1 (fr) * 1998-04-24 1999-11-04 Monsanto Company Composition concentree de compose de traitement pour plantes sous forme d'acide
WO2000053018A1 (fr) * 1999-03-11 2000-09-14 Ecoval Corporation Compositions herbicides
WO2000067573A1 (fr) * 1999-05-05 2000-11-16 Victorian Chemicals International Pty Ltd Composition d'adjuvant destinee a des substances chimiques utilisees en agriculture
WO2003090531A1 (fr) * 2002-04-24 2003-11-06 Basf Aktiengesellschaft Utilisation d'alcoxylates definis en tant qu'adjuvants dans le domaine de la technique agricole
US6756344B2 (en) 2000-02-23 2004-06-29 Victorian Chemicals International Pty Ltd Plant growth hormone compositions
WO2006035983A1 (fr) * 2004-09-27 2006-04-06 Kao Corporation Préparation herbicide
US7060659B2 (en) 2000-10-17 2006-06-13 Victorian Chemicals International Pty Ltd Herbicide composition
EP2138041A1 (fr) 2008-06-26 2009-12-30 Basf Se Un procédé d'amélioration de la résistance à l'entraînement par la pluie du glyphosate
EP2138042A1 (fr) 2008-06-26 2009-12-30 Basf Se Un procédé d'amélioration de la résistance à l'entraînement par la pluie du glyphosate
WO2009130282A3 (fr) * 2008-04-24 2010-06-17 Basf Se Suspensions concentrées contenant de la cyclodextrine, leur procédé de préapartion et leur utilisation
WO2010036996A3 (fr) * 2008-09-29 2011-03-24 Monsanto Technology Llc Formulations de glyphosate contenant des tensioactifs amidoalkylaminés
US8263529B2 (en) 2004-09-27 2012-09-11 Kao Corporation Herbicide composition
EP1721523A3 (fr) * 2000-05-19 2013-01-23 Monsanto Technology, LLC Formulations pesticides aqueuses et nouveaux surfactants
WO2020025393A1 (fr) 2018-07-30 2020-02-06 Bayer Aktiengesellschaft Combinaisons contenant du pva et certains herbicides ayant des propriétés améliorées
WO2020025394A1 (fr) 2018-07-30 2020-02-06 Bayer Aktiengesellschaft Compositions herbicides à propriétés améliorées
US11452289B2 (en) 2016-05-11 2022-09-27 Monsanto Technology Llc Glyphosate formulations containing amidoalkylamine surfactants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2790642A1 (fr) * 1999-03-08 2000-09-15 Aventis Cropscience Sa Nouvelles compositions pesticides et/ou regulatrices de croissance
EP2457890A1 (fr) * 2010-11-29 2012-05-30 Cognis IP Management GmbH Compositions de biocide comportant des produits d'alkoxylation de dérivés de l'alcool isoamylique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990175A (en) * 1989-06-13 1991-02-05 Dow Corning Corporation Foliar applied herbicidal compositions containing a silicone glycolsilicone alkane terpolymer adjuvant
US5078782A (en) * 1986-04-24 1992-01-07 Berol Nobel (Suisse) S.A. Pesticidal concentrate compositions
US5258359A (en) * 1991-08-02 1993-11-02 Monsanto Company Glyphosant-containing herbicidal compositions comprising acetylenic diol rainfastness enhancing agents

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1198455B (it) * 1985-10-31 1988-12-21 Staupfer Chemical Co Metodo e composizione per aumentare l'attivita' erbicida di sali di n-fosfonometilglicina
AU650091B2 (en) * 1991-02-08 1994-06-09 Monsanto Europe S.A. Glyphosate compositions and their use
CA2074993A1 (fr) * 1991-08-02 1993-02-03 Miguel Molina Dayawon Compositions herbicide contenant du glyphosate, a efficacite amelioree
MY111437A (en) * 1992-07-31 2000-05-31 Monsanto Co Improved glyphosate herbicide formulation.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078782A (en) * 1986-04-24 1992-01-07 Berol Nobel (Suisse) S.A. Pesticidal concentrate compositions
US4990175A (en) * 1989-06-13 1991-02-05 Dow Corning Corporation Foliar applied herbicidal compositions containing a silicone glycolsilicone alkane terpolymer adjuvant
US5258359A (en) * 1991-08-02 1993-11-02 Monsanto Company Glyphosant-containing herbicidal compositions comprising acetylenic diol rainfastness enhancing agents

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP0854676A4 *
WEED SCIENCE, Volume 25, No. 3, issued May 1977, WYRILL et al., "Glyphosate Toxicity to Common Milkweed and Hemp Dogbane as Influenced by Surfactants", pages 275-287. *

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WO1998035553A1 (fr) * 1997-02-14 1998-08-20 Imperial Chemical Industries Plc Compositions tensioactives agrochimiques
AU733973B2 (en) * 1997-02-14 2001-05-31 Croda International Plc Agrochemical surfactant compositions
US6413908B1 (en) 1997-02-14 2002-07-02 Imperial Chemical Industries Plc Agrochemical surfactant compositions
KR100497922B1 (ko) * 1997-02-14 2005-06-29 임페리알 케미칼 인더스트리즈 피엘씨 농약 계면활성제 조성물
WO1999055155A1 (fr) * 1998-04-24 1999-11-04 Monsanto Company Composition concentree de compose de traitement pour plantes sous forme d'acide
US6207617B1 (en) 1998-04-24 2001-03-27 Monsanto Compant Concentrate composition of plant treatment compound in acid form
WO2000053018A1 (fr) * 1999-03-11 2000-09-14 Ecoval Corporation Compositions herbicides
WO2000067573A1 (fr) * 1999-05-05 2000-11-16 Victorian Chemicals International Pty Ltd Composition d'adjuvant destinee a des substances chimiques utilisees en agriculture
US7314848B1 (en) 1999-05-05 2008-01-01 Victorian Chemicals International Pty Ltd. Adjuvant composition for chemicals used in agriculture
US6756344B2 (en) 2000-02-23 2004-06-29 Victorian Chemicals International Pty Ltd Plant growth hormone compositions
US10736325B2 (en) 2000-05-19 2020-08-11 Monsanto Technology Llc Surfactants and formulations
EP1721523A3 (fr) * 2000-05-19 2013-01-23 Monsanto Technology, LLC Formulations pesticides aqueuses et nouveaux surfactants
US7060659B2 (en) 2000-10-17 2006-06-13 Victorian Chemicals International Pty Ltd Herbicide composition
WO2003090531A1 (fr) * 2002-04-24 2003-11-06 Basf Aktiengesellschaft Utilisation d'alcoxylates definis en tant qu'adjuvants dans le domaine de la technique agricole
CN100370900C (zh) * 2002-04-24 2008-02-27 巴斯福股份公司 特定醇烷氧基化物在农业技术领域中作为辅助剂的用途
EA011649B1 (ru) * 2002-04-24 2009-04-28 Басф Акциенгезельшафт Композиция на основе алкоксилатов спиртов и их применение в качестве адъюванта в области агротехники
AU2003232505B2 (en) * 2002-04-24 2009-08-27 Basf Aktiengesellschaft Use of defined alcohol alkoxylates as adjuvants in the agrotechnical field
EA015423B1 (ru) * 2002-04-24 2011-08-30 Басф Се Применение определенных алкоксилатов спиртов в качестве адъюванта в области агротехники
US8877681B2 (en) 2002-04-24 2014-11-04 Basf Se Use of specific alcohol alkoxylates as an adjuvant for agrotechnical applications
EP2181593A1 (fr) * 2002-04-24 2010-05-05 Basf Se Utilisation d'alkoxylates d'alcool définis comme adjuvants pour le domaine agrotechnique
US8129312B2 (en) 2002-04-24 2012-03-06 Basf Se Use of defined alcohol alkoxylates as adjuvants in the agrotechnical field
AU2009240808B2 (en) * 2002-04-24 2011-08-04 Basf Aktiengesellschaft Use of defined alcohol alkoxylates as adjuvants
WO2006035983A1 (fr) * 2004-09-27 2006-04-06 Kao Corporation Préparation herbicide
CN102302000A (zh) * 2004-09-27 2012-01-04 花王株式会社 除草剂组合物
US8263529B2 (en) 2004-09-27 2012-09-11 Kao Corporation Herbicide composition
WO2009130282A3 (fr) * 2008-04-24 2010-06-17 Basf Se Suspensions concentrées contenant de la cyclodextrine, leur procédé de préapartion et leur utilisation
EP2138041A1 (fr) 2008-06-26 2009-12-30 Basf Se Un procédé d'amélioration de la résistance à l'entraînement par la pluie du glyphosate
EP2138042A1 (fr) 2008-06-26 2009-12-30 Basf Se Un procédé d'amélioration de la résistance à l'entraînement par la pluie du glyphosate
US10925284B2 (en) 2008-09-29 2021-02-23 Monsanto Technology Llc Glyphosate formulations containing amidoalkylamine surfactants
WO2010036996A3 (fr) * 2008-09-29 2011-03-24 Monsanto Technology Llc Formulations de glyphosate contenant des tensioactifs amidoalkylaminés
US11925179B2 (en) 2008-09-29 2024-03-12 Monsanto Technology Llc Glyphosate formulations containing amidoalkylamine surfactants
US11452289B2 (en) 2016-05-11 2022-09-27 Monsanto Technology Llc Glyphosate formulations containing amidoalkylamine surfactants
US12201111B2 (en) 2016-05-11 2025-01-21 Monsanto Technology Llc Glyphosate formulations containing amidoalkylamine surfactants
WO2020025394A1 (fr) 2018-07-30 2020-02-06 Bayer Aktiengesellschaft Compositions herbicides à propriétés améliorées
WO2020025393A1 (fr) 2018-07-30 2020-02-06 Bayer Aktiengesellschaft Combinaisons contenant du pva et certains herbicides ayant des propriétés améliorées
CN112654246A (zh) * 2018-07-30 2021-04-13 拜耳公司 具有改进性能的除草剂组合物
CN115336591A (zh) * 2018-07-30 2022-11-15 拜耳公司 具有改进性能的除草剂组合物
CN112654246B (zh) * 2018-07-30 2023-01-03 拜耳公司 具有改进性能的除草剂组合物
TWI837152B (zh) * 2018-07-30 2024-04-01 德商拜耳廠股份有限公司 經改良性質的除草劑組成物
US12342814B2 (en) 2018-07-30 2025-07-01 Bayer Aktiengesellschaft Herbicide compositions with improved properties
US12342815B2 (en) 2018-07-30 2025-07-01 Bayer Aktiengesellschaft Combinations containing PVA and certain herbicides with improved properties

Also Published As

Publication number Publication date
CA2224364A1 (fr) 1997-01-03
EP0854676A4 (fr) 2000-03-15
AU696607B2 (en) 1998-09-17
JP3980640B2 (ja) 2007-09-26
AU6386396A (en) 1997-01-15
EP0854676A1 (fr) 1998-07-29
NZ312352A (en) 1999-11-29
JPH11507673A (ja) 1999-07-06

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