IE893949A1 - Improved herbicide formulations and their use - Google Patents

Abstract

A herbicidal composition comprising a herbicidally effective amount of an agriculturally acceptable herbicide, humectant, and silicone surfactant optionally with inert adjuvants and water A method of using such composition for killing and controlling weeds is also disclosed.

Description

IMPROVED HERBICIDE FORMULATIONS AND THEIR USE BACKGROUND This invention relates to a method and composition for enhancing the efficacy of herbicides and in particular herbicides selected from the group consisting of acifluorfen, its agriculturally acceptable salts, oxyflourfen, lactofen, imazaquin and the agriculturally acceptable salts thereof, N-phosphonomethlyglycine and its agriculturally acceptable salts thereof, mixtures thereof and the like.

This invention also relates to a ready-touse composition comprising an enhanced delivery system for herbicides.

Herbicides may be applied to plants in a variety of methods including different formulations.

Of these various methods, use of liquid and dry compositions are quite desirable. The particular formulation desired and resulting efficacy enhancement will greatly depend upon the weed species to be treated, environmental conditions, the geographical area and the climate of the area at the time of treatment.

In many areas of the world, it is highly desirable to apply a herbicide composition having rainfastness quality (adherence of the herbicide to foliage when rain occurs) in areas of high rainfall amounts or under conditions and timing where rainfall is highly likely following application of a herbicide. Furthermore, there is a need for herbicide -2- 09-21(2873)A compositions which can better penetrate vegetation having a relatively thick wax coating.

Use of compostions of this invention produces increased herbicide efficacy particularly in applications of a herbicide in accordance with this invention on rhizome johnsongrass, a narrowleaf perennial, and seedling johnsongrass, as well as barnyardgrass and downy brome which are narrowleaf annuals.

Glyphosate (N-phosphonomethlyglycine) is well known as a foliage-acting herbicide. In the free acid form, glyphosate has low water solubility; and because of this, commercial formulations contain a water-soluble salt of glyphosate. For example, in Roundup® herbicide, sold as a concentrate, glyphosate is formulated as the isopropylamine salt.

U.S. Patents 3,799,758 issued on March 26, 1974 and 4,405,531 issued on September 20, 1983 disclose derivatives of N-phosphonomethylglycine and the use of N-phosphonomethylglycine, its salts and derivatives thereof as herbicides and herbicidal compositions thereof. U.S. Patent 4,315,765 issued on March 15, 1983 discloses trimethylsulfonium and trimethylsulfoxonium salts of N-phosphonomethylgly25 cine and their use as herbicides and herbicidal compositions. Iminourea and substituted iminourea salts such as guanidinium and aminoguanidinium salts of N-phosphonomethylglycine are also examples of known herbicides .

The use of humectants with certain herbicides is disclosed in Additives in Herbicide Formulations, Andress G. Kanallopoulos, Sandos, Ltd. -3- 09-21(2873)A Agrochemical Department Switzerland Chemistry and Industry, 7 December 1974, which discloses on page 352 that humectants improve penetration of herbicides into plant leaves by preventing drying of spray deposit, thereby increasing the effective penetration time. This article discloses that glycerol has been used as a humectant with 2,4-D and other herbicides. Other glycols disclosed are ethylene glycol and propylene glycol, and polyhdric alcohols in mixtures with free fatty acids and dimethylsulfoxide.

Polymeric compounds are reported to be humectants which according to this article includes Carbowax, sucrose, molasses and polypropylenediol.

In Comparison of Urea Foliar Sprays Containing Hydrocarbon or Silicone Surfactants with Soil Applied Nitrogen in Maintaining the Leaf Nitrogen Concentration of Prune Trees, D.R. Leece et. al. J. Amer. Soc. Hor Sci. 104(5):644-648 1979 disclose the use of a nonionic silicone surfactant, L-77 (organosilicone block copolymer - Union Carbide New York, the nonionic hydrocarbon surfactant (X-77), and a free fatty acid and isopropanol with the humectant glycerol in urea fertilizer foliar sprays on prune trees. Compositions and use are also disclosed for glycerol and L-77 in this article.

Monsanto Company of St. Louis, Missouri U.S.A. sells Roundup® herbicide EPA Registration No. 524-308-AA (label booklet 1987-4) which is a commercial formulation of the isopropylamine salt of N-phosphonomethylglycine. The formulation also contains an ethoxylated amine surfactant, inert adjuvants and water.

The use of an organosilicone surfactant, such as Silwet L-77 in tank mixes with commercially -4- 09-21(2873)A purchased Roundup® herbicide at times improves the rainfastness of the resulting formulation of Roundup® on some species of weeds. However, Silwet L-77 is antagonistic to Roundup® herbicide in such tank mixes with Roundup® herbicide when rainfall does not occur after a Roundup® compostion containing Silwet L-77 (without added humectant) has been applied to many plants, particularly on narrowleaf species.

Monsanto sells Pulse” penetrant (which is 10 Silwet L-77) for use with Roundup® herbicide and discloses on the Pulse label that the addition of Pulse can reduce the requisite rainfree period for Roundup® herbicide from 4-6 hours to 2 hours on perennial ryegrass when label recommended rates of Roundup® herbicide and Pulse are sprayed on dry foliage.

Australian Patent Application AU-A-64552/86 published May 7, 1987 discloses herbicide compositions comprising (a) an herbicidally effective amount of an agriculturally acceptable salt of N-phosphonomethylglycine, (b) at least one humectant having a moisture capacity substantially equivalent to that of sorbitol; (c) inert adjuvants; and (d) water; wherein the ratio of (a) to (b) ranges from about 1:33 to about 5:1 by weight. A herbicidal method of use of such compositions is also disclosed. Further, at page 3, this published patent applicaiton discloses that suitable humectants can be employed to keep a salt of N-phosphonomethylglycine moist over a longer period of time on the foliage of plants, thereby enabling it to be absorbed into the foliage in a greater quantity and at a higher rate than would otherwise be possible. -5- 09-21(2873)A L. L. Jansen, Enhancement of Herbicides by Silicone Surfactants Volume 21, Issue 2 (March 1973), WEED SCIENCE, discloses that in a comparative evaluation of adjuvant effects in eight species, nonionic silicone glycol surfactants enhanced the activity of six herbicides to a greater extent than a standard organic surfactant, where cationic amino silicone surfactants enhanced to a lesser extent.

Great Britain Patent Number 1,255,249 to 10 Dow Corning Corporation, published December 1, 1971, discloses herbicide compostions employing silicone glycol copolymers. Here, general utility of a large number of adjuvants is professed, as exemplified by two generic silicone glycol formulas which embrace structures having both diorganosiloxane units and alkyl-glycol siloxane units. There is also provided a wide-ranging list of suitable herbicides. This reference, however, provides little direction to those skilled in the art as to which particular silicone glycol structures are to be advantageously combined with specific herbicides, save for two examples employing a triazine herbicide in conjunction with an adjuvant having 1.8 siloxy units and bearing a glycol chain having 12 ethylene oxide units.

In addition to the herbicidal enhancement provided by the activity-increasing adjuvants discussed above, it is often important that herbicide formulations retain a significant degree of activity when plants treated therewith are exposed to rain shortly after application, this being a definition of the degree of rainfastness. This is particularly important for water-soluble foliar-applied herbicides, such as glyphosate salts. -6- 09-21(2873)A While prior art tank mix formulations of Roundup® have included added glycol humectants, or have included Silwet L-77 without added glycerol, a need exists for a formulation of N-phosphonomethyl5 glycine or an agriculturally acceptable salt thereof or mixtures thereof which will provide the advantages of using an organosilicone such as Silwet L-77 without antagonism toward the N-phosphonomethylglycine based herbicide under both rainfall and no rainfall conditions following application of a compostion of this invention to plant foliage.

OBJECTS It is an object of the invention to provide an agriculturally acceptable herbicidal composition having improved efficacy particularly for herbicidal compositions comprising herbicide, inert adjuvant(s), water, humectant, and silicone surfactant.

It is another object of the invention to provide a glyphosate herbicidal composition having improved efficacy under rainfall or no rainfall conditions with less antagonism toward the herbicide active ingredient than when a silicone surfactant is present in the formulation.

It is yet another object of the invention to provide a delivery system for enhancing the efficacy of herbicidal compositions containing a herbicide.

It is yet an additional object of the invention to make a herbicide more effective in maintaining contact with the locus of application, e.g., on the plant foliage. -7- 09-21(2873)A It is still yet another object of the invention to provide a herbicidal composition comprising an efficacy increasing amount of a humectant and silicone surfactant.

It is yet an additional object of this invention to provide a herbicidal method of use of such compositions as described above.

SUMMARY OF THE INVENTION The above and other objects are met in this 10 invention which provides a novel method and compostion for enhancing the efficacy of herbicides, in particular foliar applied herbicides and in more particular herbicides selected from the group consisting of acifluorfen,5-(2-chloro-a,a,a-tri15 fluoro-p-tolyloxy)-2-nitrobenzoic acid and agriculturally acceptable salts thereof; oxyfluorfen, 2-chloro-l-(3-ethoxy-4-nitrophenoxy)-4-(tri fluoromethyl) benzene; lactofen, 1-(carboethoxy)ethyl -[2-chloro-4-(trifluoromethyl) phenoxyl]-2-nitro20 benzoate; imazaquin 2-[4,5-dihydro-4-methyl-4-(1methylethyl)-5-oxo-lH-imidazol-2-yl]-3-quinoline carboxylic acid and agriculturally acceptable salts thereof; N-phosphonomethylglycine and/or agriculturally acceptable salts thereof, derivatives thereof, mixtures thereof and the like.

DETAILED DESCRIPTION OF THE INVENTION The invention herein comprises a herbicidal composition comprising a herbicidally effective amount of a herbicide and in particular a herbicide selected from the group consisting of acifluorfen, -(2-chloro-a, a ,a-trifluoro-p-tolyloxy-2-nitrobenzoic acid and agriculturally acceptable salts thereof, -8- 09-21(2873)A (see U.S. Patent 3,979,437); oxyfluorfen, 2-chloro1- (3-ethoxy-4-nitrophenoxy)-4-(tri fluoromethyl) benzene; lactofen, 1-(carboethoxy) ethyl 5-[2-chloro4- (tri fluoromethyl)phenoxyl]-2-nitrobenzoate; imazaquin, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)5- oxo-lH-imidazol-2-yl]-3-quinoline carboxylic acid and the agriculturally acceptable salts thereof, N-phosphonomethylglycine or agricultually acceptable salts thereof, mixtures thereof and the like, inert adjuvant(s), water, humectant, and silicone surfactant.

Herbicide compositions herein include both package and tank mix compositions. The term agriculturally acceptable as employed herein includes agricultual, industrial and residential uses.

Herbicides which are useful in this invention include triazines, ureas, carbamates, acetamides, uracils, acetic acid or phenol derivatives, triazoles, benzoic acids, nitriles, diphenyl ethers and the like such as: Heterocyclic nitrogen/sulfur derivatives including 2-chloro-4-ethylamino-6-isopropylamino-striazine,2-chloro-4,6-bis(isopropylamino)-s-triazine; 2- chloro-4,6-bis(ethylamine)-s-triazine; 3-isopropyl25 1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide; 3- amino-l,2,4-triazole; 5-bromo-3-isopropyl-6-methyluracil; 2-(4-isopropyl-4-methyl-5-oxo-2-imdazolin-2yl-)3-quinoline carboxylic acid; isopropylamine salt of 2-(4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid; methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate; and methyl 2-(4-isopropyl-4methyl-5-oxo-2-imidazolin-2-yl)-p-toluate; and further including acids/esters/alcohols such as (2, 2-dichloropropionic acid; -9- 09-21(2873)A 2-methyl-4-chloropheno-xyacetic acid; 2,4-dichlorophenoxyacetic acid; methyl-2-[4-(2,4-dichlorophenoxy) phenoxy] propionate; 3-amino-2,5-dichlorobenzoic acid; 2-methoxy-3, 6-dichlorobenzoic acid; 2,3,6-trichloro5 phenylacetic acid; N-l-napthylphthalamic acid; sodium 5-[2-chloro-4-(trifluoromethyl)phenoxyj-2-nitrobenzoate, 4,6-dinitro-o-sec-butylphenol; butyl 2-[-[(tri fluoromethyl)-2-pyridinyl)oxy]-phenoxy]propanoate; and cyclohexanediones, such as (±)-2-(ΙΙΟ ethoxyiminobutyl)-5-[2-( ethylthio)propyl]-3-hydroxycyclohex-2-enone, and [(3,5,6-trichloro-2-pyridyloxyacetic acid and ethers such as 2,4-dichlorophenyl-4nitrophenyl ether; 2-chloro-trifuluorop-tolyl-3ethoxy-4-nitrodiphenyl ether; 5-(2-chloro-4-trifluro15 methylphenoxy)-N-methyl-sulfonyl 2-nitro-benzamide; 11-(carboethoxy) ethyl 5-[2-chloro-4-(trifluoromethyl) phenoxy]-2-nitro-benzoate and other diphenylethers and other miscellaneous herbicides such as 2,6-dichlorobenzonitrile, monosodium acid methanearsonate; disodium methanearsonate; 2-(2-chlorophenyl)methyl-4, 4-dimethyl-3-isoxazolidinone.

Other herbicides useful for practicing the invention herein include fosamine ammomium, haloxyfop, imazapyr, mefluidide, metsulfuron methyl, picloram, guizalofop ethyl and imidazolinones.

The above compounds are intended merely as representative of the types of compounds which may be employed in this invention. N-phosphonomethylglycine itself may be employed in this invention or option30 ally any agriculturally acceptable salt, amide, ester, or derivative thereof, mixtures of one of more -10- 09-21(2873)A agriculturally acceptable salt and N-phosphonomethylglycine may be employed.

Typical agriculturally acceptable salts which may be employed include those disclosed in U.S.

Patents 3,799,758; 4,405,531; 4,315,765. Preferred salts include the isopropylamine, sodium, ammonium, trimethylsulfonium and guanidine salts. Other compounds further representative of this class of compounds are those herbicidally active compounds disclosed in U.S. Patents Numbers, 3,455,675; 3,799,758; 3,977,860; 3,868,407; 4,315,765 and 4,397,676.

Illustrative suitable humectants which may be employed in this invention includes those compounds which absorb water substantially equivalent to glycerin. Suitable humectants include sorbitol, polyethylene glycol and polypropylene glycol, propylene glycol, triethylene glycol, glycerin, sodium stearate, microcrystalline cellulose, homolinear polymers of ethylene oxide and soluble collagen, sold under the trademark Collasol by Croda Inc., lactic acid and salts thereof, cane molasses, sodium lactate and the like.

Illustrative suitable silicone surfactants useful in this invention comprise organosilicone surfactants and polyaklylene oxide modified dimethylpolysiloxane copolymers which are sold under the trademark Silwet, a trademark of Union Carbide Corporation, U.S.A. These are surface active materials and contain discrete hydrophilic (water-loving) and hydrophobic (water-hating) segments. These products have the general formula: -11- 09-21(2873)A wherein a ranges from 3 to about 24, b ranges from 0 to about 15, x is in the range from 0 to 3 and y ranges from 1 to 5 and in which Z can be hydrogen or a lower alkyl radical having 1-3 carbon atoms or an acyl group having 2 to 4 carbon atoms.

Silwet silicone surfactants useful in this invention include those described in a trade brochure by Union Carbide entitled SILICONES FOR THE AGRICULTURAL INDUSTRY SUI-356, 6/84, 5M and Surface Active Copolymers also by Union Carbide SUI-394A, 7/85-5M, both of which are incorporated herein in their entirety by reference.

Other suitable illustrative silicone surfactants which may be employed herein include SF-1188 (General Electric Company, Silicone Products Division, Rubber & Fluid Products Department, Waterford, NY 12188), Silwet L-7607, and Dow Corning Corporation, Midland, MI silicone glycols Q2-5309, Q2-5152, Q2-5852 and Q2-5853 mixtures thereof and the like.

Compounds of Formula (I) are particularly described in U.S. Patent 3,299,112 issued to Donald L. Bailey on January 17, 1967 which is incorporated herein in its entirety by reference. A particularly desired siloxane wetting agent useful herein is shown having the formula Me3SiO[MeO(C2H4O)7C3H6SiMeO] SiMe3. -12- 09-21(2873)A Also useful herein as a silicone surfactant is a silicone glycol of the average structure Me I Me3SiO(SiO)SiMe3 (II) I R(OCH2CH2)m0Z wherein Me hereinafter denotes a methyl radical and R is a divalent alkylene group having 2 to 6 carbon atoms, such as ethylene, trimethylene, tetramethylene or hexamethylene, m can be 3 to 24. It is preferred that R is a trimethylene group. In the above formula, Z is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 cardon atoms.

Preferably, Z is an acetoxy group.

The silicone glycols described above are known in the art and may be prepared by coupling the corresponding allyl-terminated glycol to a bis-siloxane structure having a hydrogen attached to the central silicon atom, said structure being Me I Me3SiO(SiO)SiMe3 (III) I H Generally, the coupling is accomplished in the presence of a platinum catalyst. The skilled artisan will recognize that, in such coupling reactions, a fraction of the allyl-terminated glycol is not converted and will remain as an impurity in the final silicone glycol product. Herbicide compositions may contain such impurities and still be within the scope of the present invention.

Silicone glycol-silicone alkane terpolymers also have utility as a silicone surfactant in the -13- 09-21(2873)A present invention. These compounds may be represented by the average formula R R I I QR2SiO(SiR2O) (SiO) (SiO) SiR2Q (IV) x I y I 2 A G wherein R is independently selected from alkyl radicals having 1 to 6 carbon atoms; A is a linear or branched alkyl radical having 7 to 30 carbon atoms; G is a glycol moiety having the formula -R’ (OCH2CH2)mOZ, in which R' is a divalent alkylene group having 1 to 6 carbon atoms, Z is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 carbon atoms and m is 8 to about 100; Q is independently selected from the group consisting of said alkyl radical A, said glycol moiety G and said alkyl radical R; x is 0 to 100, y is 0.1 to 25 and z is 0.1 to 50.

A highly preferred silicone glycol-silicone alkane terpolymer (II) useful in the present invention as a silicone surfactant has the average structure Me Me 1 . 1 .

Me3SiO(SiO)q,θ4(SiO)1,3 6SiMe 30 L CH2CH2CH2(OCH2CH2)24OC(O)CH3 (V) L (CHzhjCHa wherein Me denotes a methyl radical.

The silicone glycol-silicone alkane terpolymers described above may be prepared by methods well known in the art. Briefly, the corresponding allylterminated glycol and alpha-alkene -14- 09-21(2873 )A are coupled to an SiH-functional siloxane having the average structure R I Q'R2SiO(SiR2O) (SiRO)v+_SiR2Q’ (VI) x I H wherein Q' is R or hydrogen and R, x, y and z are as defined in Formula (IV) above.

For the highly preferred silicone glycolsilicone alkane terpolymer described above, 0.77 mole of alpha-dodecene and 1.90 moles of an allylterminated glycol having the formula CH2=CHCH2(OCH2CH2)24OC(O)CH3 are reacted with one mole of an SiH-functional siloxane having the average structure Me I Me3SiO(siO)2SiMe3 (VII) | H to form one mole of terpolymer product. Coupling is accomplished in the presence of a platinum catalyst at temperatures in the range of about 20 to about 150°C, the reaction preferably being carried out in a solvent such as toluene or isopropanol. Illustrative silicone surfactants prepared and utilized to illustrate this invention are hereinafter referred to as fluids.

In addition to the aforementioned components, the compositions of the present invention may also contain other herbicide adjuvants commonly employed in the art. Examples of such adjuvants include crop oil concentrate, ORTHO X-77 spreader, drift control agents, such as LO-DRIFT, defoaming agents, such as D-FOAMER, compatibility agents, such -15- 09-21(2873)A as E-2 MIX, and other adjuvants well known in the herbicide art.

In order to prepare the compositions of the present invention, from about 0.1 to about 10 parts by weight of the silicone glycol-silicone alkane terpolymer (II) is thoroughly mixed with each part by weight of herbicide (I). Preferably, from 0.5 to about 5 parts by weight of (II) are employed for each part of the herbicide (I). For a given herbicide, the skilled artisan will readily arrive at a herbicidal composition having the optimum ratio of the ingredients by routine experimentation.

The above herbicidal composition may then be dispersed in water and sprayed onto plants according to the method of the present invention, described infra. Alternatively, the silicone glycol-silicone alkane terpolymer adjuvant may be added directly to a water solution or dispersion of herbicide.

The compositions of this invention may be prepared, for example, by starting with a herbicide and adding in any order the various components of the composition of this invention. For example, one may start with a commercial formulation of the isopropylamine salt of N-phosphonomethylglycine which is an aqueous concentrate containing 480 grams per liter of the isopropylamine salt of N-phosphonomethylglycine (41%) by weight.

Thereafter in any order one mixes suitable amounts (a) humectant, (b) silicone surfactant and optionally an inert adjuvant and adds any diluent water. If desired, one may prepare the composition of this invention by starting with either a herbicide -16- 09-21(2873)A or an agriculturally acceptable salt thereof, or adjuvant, or humectant, or silicone surfactant.

Water may be employed if desired in an amout desired.

While the ratios of concentrations of the 5 various components of this invention are hereinafter suggested, those skilled in the art will recognize that minor variations may be necessary to accommodate particular characteristics of acceptable herbicides which may be employed in this invention.

Typically for a herbicide concentrate of this invention, the concentration of herbicide active ingredient will be in the range from about 2 to about 70% by weight and preferably in the range from about 4 to about 40% by weight of the concentrate.

In a final application solution of the herbicide of this invention, as for example in a spray solution applied to foliage, the concentration of herbicide active ingredient will be in the range from about 0.05% to about 20% by weight and preferably in the range from about 0.15% to about 5% by weight of a final solution illustrative of this invention.

The ratio of herbicidally active ingredient to silicone surfactant will be about the same whether the composition is a concentrate or a spray.

Typically, the weight ratio of active ingredient to silicone surfactant is from about 1:30 to about 50:1 and preferably in the range from about 1:15 to about 10:1. The amount of humectant employed in the herbicide formulation is an amount sufficient to overcome (or safen) any antagonism of silicone surfactant toward the herbicide action and/or to improve rainfastness. -17- 09-21(2873)A The ratio of silicone surfactant to humectant in compositions of this invention will be about the same whether the composition is a concentrate or a spray. Typically, the weight ratio of silicone surfactant to humectant will be in the range from about 1:1 to about 1:200 and preferably in the range from about 1:5 to about 1:50.

Any humectant may be employed in this invention which provides the ability to overcome (or to safen) the antagonism of silicone surfactant , toward a herbicide active.

The ratio of herbicide active ingredient to adjuvant will depend to a great deal upon the nature and type of the herbicide active ingredient which is present in the composition. However, typically, the weight ratio of herbicide active ingredient to adjuvant is in the range from about 1:5 to about 10:1 and preferably in the range from about 1:2 to about 4:1.

The amount of water which is employed to prepare the concentrate or final application concentration, as in a spray, is adjusted as necessary. The concentrate and/or final composition may be a dry formulation.

Those skilled in the art will recognize that some departures may be made in the above ranges without significantly affecting the performance of the composition of this invention.

The phytotoxicant compositions of this invention, particularly liquids and soluble powders, preferably contain (in addition to the herbicide active, silicone surfactant, and humectant, an inert -18- 09-21(2873)A adjuvant or conditioning agent), one or more surface active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface active agent into the compositions of this invention greatly enhances their efficacy. By the term surface active agent, it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, cationic and nonionic agents can be employed with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amines, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkyl phenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the fatty acid esters of hexito anhydrides (sorbitan). Preferred dispersants are methylcellulose, polyvinylalcohol sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaph thalene sulfonates and sodium N-methyl-N-long chain acid laurates.

Suitable surfactants (adjuvants) are disclosed in U.S. Patents 3,799,758 and 4,405,531 supra both of which are incorporated herein in their entirety be reference.

A particularly preferred composition of this invention comprises the commercial formulation Roundup® herbicide, Silwet L-77, glycerine and diluent water. A particularly preferred method of -19- 09-21(2873)A this invention comprises the use of that composition as a post emergent herbicide to kill or control rhizome johnsongrass, seedling johnsongrass, barnyardgrass and downy brome.

Water dispersible powder compositions can be made containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinities, attapulgite clay and synthetic magnesium silicate. The water dispersible powder of this invention usually contain from about 5 to about 95 parts by weight of active ingredient, from about 0.25 to about 25 parts by weight of wetting agent, from about 0.25 to about 25 parts by weight of dispersant and about 4.5 to about 94.5 parts by weight of inert solid extender, all parts being by weight to the total composition. Where required, from about 0.1 to about 2.0 parts by weight of the solid inert extender can be replaced by a corrosion inhibitor or antifoaming agent or both.

Aqueous suspensions can be prepared by mixing together and grinding an aqueous slurry of a water-insoluble active ingredient in the presence of dispersing agents to obtain a concentrated slurry of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size so that when diluted and sprayed, coverage is very uniform.

Although compositions of this invention can also contain other additaments, for example fertilizers, phytotoxicants and plant growth -20- 09-21(2873)A regulants, herbicides and the like used as adjuvants or in combination with any of the above described adjuvants, it is preferred to employ the compositions of this invention along with sequential treatments with other phytotoxicants, fertilizers and the like for maximum effect. Composition of this invention can also be admixed with other materials such as fertilizers, phytotoxicants and the like and applied in a single application. Chemicals useful in combination with the active ingredients of this invention, either simultaneously or sequentially, include for example triazine, ureas, carbamates, acetamides, uracils, acetic acids, phenols, thiocarbamates, triazoles, benzoic acids, nitriles and the like.

When practicing this invention, effective amounts of herbicide, for example, amounts of herbicide which kill or control plants. For example, effective amounts of N-phosphonomethylglycine or agriculturally acceptable salts thereof or derivatives are applied to above ground portions of plants (foliage in particular). The application of liquid and particulate solid herbicidal compositions to above ground portions of plants can be carried out by conventional methods, e.g. boom and hand application including sprayers or dusters. The compostion can also be applied aerially as spray, if desired.

The application of an effective amount of the herbicide composition of the invention to a selected locus, such as a plant foliage, is essential for the practice of this invention. The amount of herbicide active ingredient to be employed is dependent upon the response desired in the plant, as well as such other factors as the plant species and -2109-21(2873 )A stage of development thereof, the amount of rainfall and the specific herbicide employed. It is believed that one skilled in the art can readily determine from the teachings of this specification including examples, the approximate application rate.

GENERAL PROCEDURE FOR EXAMPLES 1-34 The following weed species were used as indicator weeds: Common Name Scientific Name Seedling johnsongrass Rhizome johnsongrass Downy brome Barnyardgrass Velvetleaf Yellow nutsedge Crabgrass Cocklebur Redroot pigweed Sorghum halepense Sorghum halepense Bromus tectorum Echinochloa crus-galli Abutilon theophrasti Cyperus esculentus Digitaria sp.

Xanthium pennsylvanicum Amaranthus retroflexus The narrowleaf and broadleaf test weeds were seeded separately into plastic pots 10.2 cm in diameter and 7.6 cm deep with drainage holes on the bottom. The pots contained Dupo silt loam soil obtained from the St. Charles Research Farm of Monsanto Company located in St. Charles, Missouri.

Prior to use, the soil was steam sterilized at a temperature of 82° C. The soil used was either mixed with a slow release 14-14-14 fertilizer so as to prefertilize it or in some cases where the soil was not prefertilized, the soil was fertilized with a 5% commercial Rapid-Gro fertilizer solution via sub-irrigation 3 to 5 days prior to treating the plants in the pots with the chemical compositions. -22- 09-21(2873)A Seedling johnsongrass, barnyardgrass, downy brome, velvetleaf, crabgrass, cocklebur and redroot pigweed were started from seeds, rhizome johnsongrass plants were grown from rhizome pieces and yellow nutsedge from tubers. In all cases, sufficient seeds or stock propagules were planted to produce several seedlings in each pot. Approximately 7 to 10 days after seeding, the velvetleaf, cocklebur and redroot pigweed seedlings were thinned out leaving 2 to 3 healthy seedlings per pot.

After the pots were seeded, the pots were moved into the greenhouse and placed on trays with each tray holding 40 to 60 pots. The trays were lined with absorbent mats for sub-irrigation. The greenhouse temperature was maintained at 30°C during the day and 21°C during the night. Photoperiod in the greenhouse was maintained at 14 to 16 hours daylength using supplemental lighting. The seeded pots were watered via subirrigation as required.

Depending on the weed species used in a given test, the chemical treatments were applied within 14 to 21 days after planting. At that time, the narrowleaf weeds were approximately 10 to 40 cm tall while the broadleaf weeds were 2.5 to 10 cm tall.

Chemical treatments were applied postemergence with the foliage of the weeds as the locus of application using a tract sprayer equipped with a single 8001E spray nozzle. The sprayer was previously calibrated to deliver a spray volume equivalent to about 187 liters per hectare of spray solution at a spraying pressure of about 2.1 x 105 pascals (30 p.s.i.). -23- 09-21<2873)A The chemical compositions illustrative of compositions of this invention used in the tests were formulated as tank mixtures the same day of application. The formulations comprised an 5 agriculturally acceptable salt of N-phosphonemethylglycine namely the isopropylamine salt, an inert adjuvant as a surfactant, a humectant, an organosilicone surface active copolymer and water.

Rates of application based on 10 N-phosphonomethylglycine ranged from about 0.14 to 3.4 kilograms glyphosate acid equivalent per hectare. The ingredient ratios employed in the formulations were glyphosate to surfactant, about 1:0.125 to 1:1, surfactant to silicone 1:0.45 to 1:20, silicone surfactant to humectant about 1:1 to about 1:200. Rainfall treatment was applied one hour after spraying of the compositions using a rain tower calibrated to deliver approximately 6.4 mm of simulated rainfall within a period of about 15 minutes.

After application of rainfall, the treated plants were placed on carts and moved into the greenhouse. After the plants had sufficiently dried out, the pots were returned to the greenhouse trays and arranged in a a randomized complete block experimental design. Each treatment contained 3 replications. Control plants and appropriate standard treatments were provided in each test. A duplicate set of plants which received the same treatment and treated in a similar manner as the rainfall treated plants were also provided for comparison under no rain condition.

Observations of the effects of the treatments were taken within 7 to 10 days for early -24- 09-21(2873)A burndown effects and again within 21 to 28 days after treatment for longer term effects. A rating scale of 0% to 100% was used in estimating the degree of weed control with 0% having no observable effect and 100% as complete kill of the weed. The degree of burn, chlorosis, necrosis, stature reduction, and other observable effects of the treatments on plant species present in the test were taken into consideration in making the ratings.

Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations.

Examples which follow illustrate compositions and method of use of this invention.

Within some of these examples, there are comparative data obtained therewith in various columns and lines for compositions typical of prior art tank mixes comprising Roundup® herbicide wiht L-77 added, Roundup® herbicide without added Silwet L-77 and Roundup® herbicide with glycerin (but no added silicone surfactant). In these examples, a.e. acid equivalent means acid equivalent of glyphosate acid (N-phosphonomethylglycine). -25- 09-21(2873 )A EXAMPLE 1 Response of rhizome johnsongrass to Roundup® and Roundup® + L-77 tank mixture under no rain condition and after simulated rainfall and mist treatments applied one hour after application of herbicide treatment. inhibition Data show average percent growth at 14 and 28 days after treatment. Treatment Roundup® Rate (kg ae/ha) 0.28 0 .84 Mean 14 Days After Treatment Roundup® No Rainfall 10 92 51 6.4mm Rainfall 3 15 9 Light Mist 7 87 47 Roundup® No Rainfall 2 25 12 + 1% L-77 6.4mm Rainfall 10 38 24 Light Mist 8 77 42 28 Days After Treatment Roundup® No Rainfall 33 91 62 6.4mm Rainfall 10 38 24 Light Mist 18 97 58 Roundup® No Rainfall 10 28 22 + 1% L-77 6.4mm Rainfall 22 48 35 Light Mist 28 88 53 -26- 09-21(2873)A EXAMPLE 2 Response of rhizome johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin at different concentrations of glycerin in the spray mixture in the absence of simulated rainfall treatment. Data show average percent growth inhibition at 28 days after treatment.

Treatment Roundup® Rate (kg ae/ha) 0.28 0.56 0.84 Mean Roundup® 60 97 88 82 Roundup® + 1% L-77 20 35 63 39 Roundup® + 1% L-77 + 1% glycerin 43 58 71 58 Roundup® + 1% L-77 + 3% glycerin 35 78 77 63 Roundup® + 1% L-77 + 5% glycerin 72 88 92 84 Roundup® + 1% glycerin 60 100 100 87 Roundup® + 3% glycerin 62 100 100 87 Roundup® + 5% glycerin 55 100 100 85 -27- 09-21(2873)A EXAMPLE 3 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin at different glycerin concentrations in the spray mixture with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. All treatments contained Roundup® at 0.56 kg ae/ha.

Treatment Rainfall Average % Inhibition 7 DAT 21 DAT Roundup® None 75 100 6.4 mm 17 53 Roundup® + 1% L-77 None 23 45 15 6.4 mm 28 63 Roundup® + 1% L-77 None 18 45 + 1% glycerin 6.4mm 60 93 Roundup® + 1% L-77 None 33 66 + 2% glycerin 6.4mm 58 99 20 Roundup® + 1% L-77 None 82 96 + 5% glycerin 6.4mm 52 92 Roundup® + 1% L-77 None 93 100 + 10% glycerin 6.4mm 82 99 -28- 09-21(2873)A EXAMPLE 4 Repsonse of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + propylene glycol in the spray mixture with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. All treatments contained Roundup® at 0.56 kg ae/ha.

Average % Inhibition Treatment Rainfall 7 DAT 21 DAT Roundup® None 75 100 6.4 mm 17 53 Roundup® + 1% L-77 None 23 45 6.4 mm 28 63 Roundup® + 1% L-77 None 28 83 + 1% propylene glycol 6.4mm 37 83 Roundup® + 1% L-77 None 63 95 + 2% propylene glycol 6.4mm 42 90 -29- 09-21(2873)A EXAMPLE 5 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + silicone surfactant and Roundup® + silicone surfactant + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 23 days after treatment. Treatment Roundup® Rate (kg ae/ha) Rainfall 0.14 0.42 Mean Roundup® None 45 99 72 6.4 mm 5 72 38 15 Roundup® + 0.25% L-77 None 3 25 14 6.4 mm 3 72 38 Roundup® + 0.25% L-77 None 98 100 99 + 10% glycerin 6.4mm 88 98 93 Roundup® + 1% L-77 None 5 30 18 20 6.4mm 18 78 48 Roundup® + 1% L-77 None 80 99 90 + 10% glycerin 6.4mm 37 97 67 Roundup® + 0.25% SF-1188 None 7 96 52 6.4 mm 5 72 38 25 Roundup® + 0.25% SF-1188 None 94 100 97 + 10% glycerin 6.4 mm 53 96 74 Roundup® + 1% SF-1188 None 20 96 58 6.4mm 10 43 26 Roundup® + 1% SF-1188 None 97 100 98 30 + 10% glycerin 6.4mm 85 100 92 Roundup® + 10% glycerin None 57 100 78 6.4mm 0 40 20 -30- 09-21(2873 )A EXAMPLE 6 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + PEG-200 with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® None 17 100 58 6.4 mm 0 88 44 Roundup® + 0.25% L-77 None 3 22 13 15 6.4 mm 0 83 42 Roundup® + 0.25% L-77 None 43 99 71 + 5% PEG-200 6.4mm 77 98 88 Roundup® + 0.25% L-77 None 95 100 97 + 10% PEG-200* 6.4mm 68 100 84 20 Roundup® + 0.50% L-77 None 8 20 14 6.4mm 18 68 43 Roundup® + 0.50% L-77 None 12 82 47 + 5% PEG-200 6.4 mm 42 96 69 Roundup® + 0.50% L-77 None 80 100 90 25 + 10% PEG-200 6.4 mm 80 99 90 Roundup® + 1% L-77 None 22 50 36 6.4mm 42 77 59 Roundup® + 1% L-77 None 17 50 36 + 5% PEG-200 6.4mm 80 100 90 30 Roundup® + 1% L-77 None 50 97 74 + 10% PEG-200 6.4mm 65 98 82 * HO(CH2CH2O)nH 4.5 -31- 09-21(2873)A EXAMPLE 7 Response of rhizome johnsongrass to Roundup® and tank mixtures containing Roundup® + silicone SF-1188 as a silicone surfactant and Roundup® + SF-1188 + glycerin at different glycerin concentrations in the spray mixture with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.28 0.84 Mean Roundup® None 15 98 56 15 6.4 mm 2 23 12 Roundup® + 1% SF-1188* None 8 85 47 6.4 mm 2 7 4 Roundup® + 1% SF-1188 None 28 82 55 + 1.25% glycerin 6.4mm 0 52 26 20 Roundup® + 1% SF-1188 None 82 97 89 + 2.5% glycerin 6.4mm 22 80 51 Roundup® + 1% SF-1188 None 97 99 98 + 5% glycerin 6.4mm 83 98 91 Roundup® + 1% SF-1188 None 97 100 98 25 + 10% glycerin 6.4 mm 77 94 85 * SF-1188 is a silicone fluid comprising a copolymer of a polydimethylsiloxane and a polyoxyalkylene ether made and sold by General Electric Company, Silicone Products Division, Waterford, NY 12188. -32- 09-21(2873)A EXAMPLE 8 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-7607 and Roundup® + L-7606 + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments.

Data show average percent growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® None 0 98 49 6.4 mm 7 83 45 Roundup® + 1% L-7607 None 12 48 31 6.4 mm 27 87 57 Roundup® + 1% L-7607 None 37 52 44 + 1% glycerin 6.4mm 27 67 47 Roundup® + 1% L-7607 None 43 97 70 + 3% glycerin 6.4mm 38 88 63 Roundup® + 1% L-7607 None 63 100 82 + 5% glycerin 6.4mm 90 95 93 Roundup® + 1% L-7607 None 93 100 97 + 10% glycerin 6.4 mm 83 98 91 -33- 09-21(2873)A EXAMPLE 9 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + SF-1188 and Roundup® + SF-1188 + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments.

Data show average percent growth inhibition at 21 days after treatment. 10 Treatment Roundup® Rate (kg ae/ha) Rainfall 0.14 0.42 Mean Roundup® None 0 98 49 6.4 mm 7 83 45 Roundup® + 1% SF-1188* None 0 33 17 15 6.4 mm 13 76 45 Roundup® + 1% SF-1188 None 3 59 31 + 1% glycerin 6.4 mm 55 87 71 Roundup® + 1% SF-1188 None 95 96 96+ 3% glycerin 6.4mm 58 99 79 20 Roundup® + 1% SF-1188 None 100 95 97 + 5% glycerin 6.4mm 93 100 97 Roundup® + 1% SF-1188 None 93 100 97 + 10% glycerin 6.4 mm 99 100 100 -34- 09-21(2873)A EXAMPLE 10 Response of yellow nutsedge to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth treatment. Treatment inhibition at 28 days Roundup® Rate after (kg ae/ha) Rainfall 1.12 2.24 3.36 Mean Roundup® None 50 77 85 71 6.4 mm 23 47 73 47 Roundup® + 0.25% L-77 None 45 67 96 69 6.4 mm 45 82 57 61 Roundup® + 0.25% L-77 None 70 88 90 82 + 2.5% glycerin 6.4 mm 52 58 73 61 Roundup® + 0.25% L-77 None 57 85 99 80 + 5% glycerin 6.4 mm 57 67 72 65 Roundup® + 0.25% L-77 None 65 74 78 72 + 10% glycerin 6.4 mm 47 95 65 69 Roundup® + 1% L-77 None 65 75 87 76 6.4 mm 60 73 73 69 Roundup® + 1% L-77 None 67 84 80 77 + 2.5% glycerin 6.4 nun 58 70 79 69 Roundup® + 1% L-77 None 70 88 90 83 + 5% glycerin 6.4 mm 53 63 90 69 Roundup® + 1% L-77 None 89 93 99 94 + 10% glycerin 6.4 mm 77 63 92 77 -35- 09-21(2873)A EXAMPLE 11 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + sorbitol with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 23 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® None 12 97 54 6.4 mm 5 63 34 Roundup® + 0.25% L-77 None 3 7 5 6.4 mm 3 17 10 Roundup® + 0.25% L-77 None 23 93 58 + 5% sorbitol* 6.4 mm 13 85 49 Roundup® + 0.25% L-77 None 27 100 63 + 10% sorbitol 6.4mm 23 94 59 Roundup® + 10% sorbitol None 32 98 65 6.4mm 7 20 13 * CH2OH I (CHOH)4 I CH20H -36- 09-21(2873 )A EXAMPLE 12 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin at different concentrations of L-77 and glycerin in the spray mixture with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 24 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® None 15 98 56 6.4 mm 10 87 48 15 Roundup® + 0.05% L-77 None 12 38 25 6.4 mm 17 35 26 Roundup® + 0.05% L-77 None 87 99 93 + 2.5% glycerin 6.4 mm 72 100 86 Roundup® + 0.05% L-77 None 98 98 98 20 + 5% glycerin 6.4mm 85 100 92 Roundup® + 0.05% L-77 None 94 99 97 + 10% glycerin 6.4 mm 93 95 94 Roundup® + 0.10% L-77 None 8 8 8 6.4 mm 13 84 49 25 Roundup® + 0.10% L-77 None 79 100 89 + 2.5% glycerin 6.4mm 7 83 45 Roundup® + 0.10% L-77 None 98 99 99 + 5% glycerin 6.4 mm 63 99 81 Roundup® -t- 0.10% L-77 None 90 99 95 30 + 10% glycerin 6.4 mm 82 98 90 Roundup® + 0.30% L-77 None 7 18 13 6.4mm 17 87 52 Roundup® + 0.30% L-77 None 20 88 54 + 2.5% glycerin 6.4mm 18 65 42 35 Roundup® + 0.30% L-77 None 86 99 93 + 5% glycerin 6.4 mm 15 98 57 Roundup® + 0.30% L-77 None 97 99 98 + 10% glycerin 6.4 mm 52 99 75 -3709-21(2873)A EXAMPLE 13 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + silicone and Roundup® + silicone surfactant + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 21 days after treatment.

Roundup® i Rate (kg ae/ha) Treatment Rainfall 0. 14 0.42 Mean Roundup® None 2 98 60 6.4 mm 0 5 3 Roundup® + 0.25% L-77 None 0 5 3 15 6.4 mm 0 0 0 Roundup® + 0.25% L-77 None 98 100 99 + 10% glycerin 6.4 mm 93 97 95 Roundup® + 1% L-' 77 None 3 55 29 6.4mm 15 28 22 20 Roundup® + 1% L-' 77 None 78 100 89 + 10% glycerin 6.4 mm 67 100 83 Roundup® + 0.25% L-7607 None 0 12 6 6.4 mm 0 2 1 Roundup® + 0.25% L-7607 None 98 100 99 25 + 10% glycerin 6.4mm 77 98 88 Roundup® + 1% L-' 7607 None 0 32 16 6.4 mm 0 8 4 Roundup® + 1% L-' 7607 None 97 100 99 + 10% glycerin 6.4 mm 78 95 87 30 Roundup® + 0.25% SF-1188 None 0 13 7 6.4mm 0 0 0 -38- 09-21(2873)A Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® + 0.25% SF-1188 None 92 100 96 + 10% glycerin 6.4 mm 10 65 38 Roundup® + 1% SF-1188 None 0 15 8 6.4 mm 0 0 0 Roundup® + 1% SF-1188 None 95 99 97 + 10% glycerin 6.4 mm 33 97 65 Roundup® + 10% glycerin None 45 100 72 6.4mm 0 8 4 -39- 09-21(2873)A EXAMPLE 14 Response of downy brome to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin with and without simulated rainfall treatment. Simluated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth treatment.

Treatment Roundup® Roundup® + 0.25% L-77 Roundup® + 0.25% L-77 + 2.5% glycerin Roundup® + 0.25% L-77 + 5% glycerin Roundup® +0.25% L-77 + 10% glycerin Roundup® + 1% L-77 Roundup® + 1% L-77 + 2.5% glycerin Roundup® + 1% L-77 + 5% glycerin Roundup® + 1% L-77 + 10% glycerin inhibition at 28 days after Roundup® Rate (kg ae/ha Rainfall 0 .42 0.84 1.68 Mean None 15 75 100 63 6.4 mm 0 5 13 6 None 13 94 92- 66 6.4 mm 3 7 8 6 None 95 99 100 98 6.4 mm 5 18 72 32 None 97 99 99 98 6.4 mm 17 38 56 37 None 97 88 99 95 6.4 mm 58 42 70 57 None 23 23 72 39 6.4 mm 0 2 2 1 None 53 92 91 79 6.4 mm 7 2 12 7 None 95 100 99 98 6.4 mm 3 22 40 22 None 93 100 100 98 6.4 mm 23 28 73 42 -40- 09-21(2873)A EXAMPLE 15 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + humectant with and without simulated rainfall treatment. Simluated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth treatment. inhibition at 22 days after 10 Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0 .42 Mean Roundup® None 6.4 mm 8 3 99 32 54 18 Roundup® + 0.25% L-77 None · 13 3 8 15 6.4 mm 0 18 9 Roundup® + 0.25% L-77 None 93 99 96 + 5% glycerin 6.4 mm 58 97 78 Roundup® + 0.25% L-77 None 53 99 76 + 5% dextrose 6.4 mm 15 85 50 20 Roundup® + 0.25% L-77 None 97 100 98 + 5% sodium lactate* 6.4 mm 3 47 25 Roundup® + 0.25% L-77 None 52 97 74 + 5% lactic acid* 6.4 mm 7 22 14 Roundup® + 0.25% L-77 None 91 99 95 25 + 5% triethylene glycol 6.4 mm 91 98 95 Roundup® + 0.25% L-77 None 91 99 96 + 5% PEG-200 6.4 mm 57 99 78 Roundup® + 0.25% L-77 None 12 5 8 + 5% cane molasses 6.4 mm 15 30 23 30 Roundup® + 5% dextrose None 6.4 mm 13 5 97 10 55 8 * Humectants -41- - 09-21(2873)A Roundup® Rate (kg ae/ha) Treatment Rainfall 0.14 0.42 Mean Roundup® + 5% sodium None 75 100 88 lactate 6.4 mm 2 27 14 5 Roundup® + 5% lactic None 40 82 61 acid 6.4 mm 0 33 17 Roundup® + triethylene None 67 99 83 glycol 6.4 mm 0 10 5 Roundup® + 5% PEG-200 None 62 99 80 10 6.4 mm 2 25 13 Roundup® + 5% cane None 5 2 3 molasses 6.4 mm 5 2 3 -42- 09-21(2873)A EXAMPLE 16 Response of seedling johnsongrass to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + humectant at differenct concentrations of L-77 and humectant in the spray mixture without simulated rainfall treatment. Data show average percent growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment 0.14 0.42 Mean Roundup® 62 98 80 Roundup® + 0.01% L-77 13 97 55 Roundup® + 0.01% L-77 + 0.25% glycerin 5 77 41 Roundup® + 0.01% L-77 Ί- 0.50% glycerin 10 90 50 Roundup® + Ο. 01% L-77 + 1.00% glycerin 25 97 61 15 Roundup® + 0.01% L-77 + 0.25% TEG* 12 83 47 Roundup® + 0.01% L-77 + 0.50% TEG 12 93 52 Roundup® + 0.01% L-77 + 1.00% TEG 42 88 65 Roundup® + 0.025% L-77 3 68 36 Roundup® + 0.025% L-77 + 0.025% glycerin 2 45 23 20 Roundup® + 0.025% L-77 + 0.50% glycerin 2 57 29 Roundup® + 0.025% L-77 + 1.00% glycerin 15 78 46 Roundup® + 0.025% L-77 + 0.25% TEG 2 43 23 Roundup® + 0.025% L-77 + 0.50% TEG 0 55 28 Roundup® + 0.025% L-77 + 1.00% TEG 13 77 45 25 Roundup® + 0.05% L-77 2 28 15 Roundup® + 0.05% L-77 + 0.50% glycerin 0 8 4 Roundup® + 0.05% L-77 + 1.00% glycerin 2 35 18 Roundup® + 0.05% L-77 Ί- 2.50% glycerin 58 73 66 Roundup® + Ο. 05% L-77 + 0.50% TEG 0 13 7 30 Roundup® + 0.05% L-77 + 1.00% TEG 0 33 17 Roundup® + 0.05% L-77 + 2.50% TEG 25 75 50 *Triethylene glycol 09-21(2873)A Treatment Roundup® + 0.10% L-77 Roundup® + 0.10% L-77 + 0 Roundup® + 0.10% L-77 + 1 Roundup® + 0.10% L-77 + 2 Roundup® + 0.10% L-77 + 0 Roundup® + 0.10% L-77 + 1 Roundup® + 0.10% L-77 + 2 Roundup® Rate (kg ae/ha) 0.14 0.42 Mean 3 13 8 50% glycerin 2 8 5 00% glycerin 2 15 8 50% glycerin 52 92 72 50% TEG 7 2 4 00% TEG 3 2 3 50% TEG 27 78 53 -44- 09-21(2873)A EXAMPLE 17 Response of cocklebur to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin with and without simulated rainfall treatment. Simluated rainfall equivalent to 6.4mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 22 days after treatment.

Roundup® Rate (kg ae/ha) Treatment Rainfall 0.07 0.21 0.33 Mean Roundup® None 60 100 100 87 6.4 mm 0 33 57 3Ό Roundup® + 0.25% L-77 None 43 95 99 79 6.4 mm 30 80 75 62 Roundup® + 0.25% L-77 None 80 95 100 92 + 5% glycerin 6.4 mm 55 83 100 79 -4509-21(2873 )A EXAMPLE 18 Response of crabgrass and pigweed to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin in the absence of simulated rainfall treatment. Data show average percent growth inhibition at 20 days after treatment.

Treatment Average % Inhibition Glyphosate Rate (kg ae/ha) Crabgrass Pigweed Roundup® 0.07 20 0 0.21 96 100 0.35 98 100 0.49 100 100 ———- Mean 76 75 Roundup® + 0.25% L-77 0.07 0 75 0.21 33 100 0.35 72 100 0.49 78 100 • Mean 46 94 Roundup® + 0.25% L-77 0.07 67 100 + 5% glycerin 0.21 97 95 0.35 100 100 0.49 100 100 Mean 91 99 -46- 09-21(2873)A EXAMPLE 19 Response of downy brome and velvetleaf to Roundup® and tank mixtures containing Roundup® + L-77 and Roundup® + L-77 + glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 6.4 mm of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 23 days after treatment.

Treatment Weed Species Roundup® Rate (kg ae/ha) Rainfall 0.25 0.49 Mean Roundup® Downy brome None 83 93 88 6.4 mm 68 63 66 Velvetleaf None 50 77 63 6.4 mm 0 2 1 Roundup® Downy brome None 63 82 72 + 0.25% L-77 6.4 mm 47 77 62 Velvetleaf None 80 80 80 6.4 mm 90 90 90 Roundup® Downy brome None 100 100 100 + 0.25% L-77 6.4 mm 99 100 100 + 5% glycerin Velvetleaf None 47 97 72 6.4 mm 98 98 98 -47- 09-21(2873)A EXAMPLE 20 Response of seedling johnsongrass to glyphosate formulations containing quaternary ammonium surfactants at different glyphosate to surfactant ratios with and without L-77 and/or glycerin and in the absence of simulated rainfall treatment. Data show average growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment 0.14 0.42 Mean Roundup® 85 99 93 Roundup® + 0.25% L-77 20 63 42 Roundup® + 0.25% L-77 + 5% glycerin 97 100 98 MON-0139/MON-0818*** (2:1) 78 99 89 15 MON-0139/MON-0818 + 0.25% L-77 15 86 51 ΜΘΝ-0139/ΜΟΝ-0818 + 0.25% L-77 + 5% glycerin 93 98 96 ΜΟΝ-0139/ΜΘΝ-0818 (4:1) 73 99 86 MON-0139/MON-0818 + 0.25% L-77 18 47 32 20 ΜΟΝ-0139/ΜΘΝ-0818 + 0.25% L-77 + 5% glycerin 94 100 97 MON-0139/MON-0818 (8:1) 37 100 68 ΜΘΝ-0139/ΜΟΝ-0818 + 0.25% L-77 10 38 24 25 ΜΘΝ-0139/ΜΟΝ-0818 + 0.25% L-77 + 5% glycerin 99 100 100 MON-0139/Arquad* T50 (2:1) 87 100 93 ΜΘΝ-0139/Arquad T50 + 0.25% L-77 17 76 46 30 MON-O139/Arquad T50 + 0.25% L-77 + 5% glycerin 99 100 99 MON-0139/Arquad T50 (4:1) 90 100 95 MON-0139/Arquad T50 + 0.25% L-77 13 53 33 MON-0139/Arquad T50 + 0.25% L-77 + 5% glycerin 98 100 99 MON-0139/Arquad T50 (8:1) 43 100 72 35 MON-0139/Arquad T50 + 0.25% L-77 10 43 27 MON-O139/Arquad T50 + 0.25% L-77 98 100 99 -48- 09-21(2873 )A Roundup® Rate (kg ae/ha) Treatment 0.14 0 .42 Mean MON-013 9/Ethoquad ** 0-25 (2:1) 72 99 86 MON-0139/Ethoquad 0-25 + 0 •25% L-77 18 84 51 MON-O139/Ethoquad 0-25 + 0 • 25% L-77 62 100 81 + 5% glycerin MON-0139/Ethoquad ** 0-25 (4:1) 48 98 73 MON-0139/Ethoquad 0-25 + 0 •25% L-77 18 33 26 M0N-0139/Ethoquad 0-25 + 0 • 25% L-77 95 100 98 + 5% glycerin MON-013 9/Ethoquad ** 0-25 (8:1) 20 99 59 MON-013 9/Ethoquad 0-25 + 0 •25% L-77 7 33 20 MON-0139/Ethoquad 0-25 + 0 .25% L-77 99 100 99 + 5% glycerin CH3 l + Formula * = C18H35—N —(CH2CH2O) H Cl | m+n total 15 (CH2CH2O)mH CH3 l + Formula ** = R—N—CH3 Cl I CH3 R is from tallow Formula *** = R-NC^ ^^(CH2CH2O)mH H(CH2CH2O) ^-(CH2CH2O)nH m+n+p ~ 20 R is from tallow -4909-21(2873)A Treatment MON-0139/Arquad B-100* (2:1) MON-0139/Arquad B-100 + 0.25% ΜΘΝ-0139/Arquad B-100 + 0.25% + 5% glycerin MON-0139/Arquad B-100 (4 :1) MON-0139/Arquad B-100 + 0.25% MON-0139/Arquad B-100 + 0.25% + 5% glycerin MON-O139/Arquad B-100 (8 :1) MON-O139/Arquad B-100 + 0.25% MON-O139/Arquad B-100 .+ 0.25% + 5% glycerin Roundup® Rate (kg ae/ha) 0.14 0.42 Mean 74 100 87 L-77 27 85 56 L-77 93 99 96 77 100 88 L-77 25 73 49 L-77 99 100 100 33 100 67 L-77 23 73 48 L-77 99 100 100 ch2—0 1 + R—N—CH3 Cl’ CH3 R = fatty acid -50- 09-21(2873)A EXAMPLE 21 Response of velvetleaf to glyphosate formulations containing quaternary ammonium surfactants at different glyphosate to surfactant ratios with and without L-77 and/or glycerin and in the absence of simulated rainfall treatment. Data show average growth inhibition at 21 days after treatment.

Roundup® Rate (kg ae/ha) Treatment 0.35 0.56 Mean 10 Roundup® 27 77 52 Roundup® + 0.25% L-77 72 87 79 Roundup® + 0.25% L-77 + 5% glycerin 68 94 81 MON-0139/MON-0818 (2:1) 38 75 57 MON-0139/MON-0818 + 0.25% L-77 68 82 75 15 MON-0139/MON-0818 + 0.25% L-77 + 5% glycerin 83 91 87 MON-0139/MON-0818 (4:1) 23 70 47 MON-0139/MON-0818 + 0.25% L-77 68 87 78 20 MON-0139/MON-0818 + 0.25% L-77 + 5% glycerin 77 87 82 MON-0139/MON-0818 (8:1) 20 68 44 MON-0139/MON-0818 + 0.25% L-77 73 87 80 25 MON-0139/MON-0818 + 0.25% L-77 + 5% glycerin 73 87 80 MON-O139/Arquad T50 (2:1) 25 78 52 MON-O139/Arquad T50 + 0.25% L-77 25 58 42 MON-O139/Arquad T50 + 0.25% L-77 + 5% glycerin 73 93 83 MON-0139/Arquad T50 (4:1) 3 72 38 30 MON-0139/Arquad T50 + 0.25% L-77 55 75 65 MON-O139/Arquad T50 + 0.25% L-77 + 5% glycerin 65 88 77 MON-0139/Arquad T50 (8:1) 5 60 32 MON-0139/Arquad T50 + 0.25% L-77 60 77 68 35 MON-0139/Arquad T50 + 0.25% L-77 + 5% glycerin 75 83 79 -51- 09-21(2873)A Roundup® Rate (kg ae/ha) Treatment 0.35 0.56 Mean M0N-0139/Ethoquad 0-25 (2:1) 15 80 48 MON-0139/Ethoquad 0-25 + 0.25% L-77 52 73 62 5 MON-0139/Ethoquad 0-25 + 0.25% L-77 + 5% glycerin 77 88 82 MON-O139/Ethoquad 0-25 (4:1) 12 68 40 M0N-0139/Ethoquad 0-25 + 0.25% L-77 62 77 69 10 MON-O139/Ethoquad 0-25 + 0.25% L-77 + 5% glycerin 77 85 81 MON-O139/Ethoquad 0-25 (8:1) 7 47 27 MON-O139/Ethoquad 0-25 + 0.25% L-77 73 90 82 MON-O139/Ethoquad 0-25 + 0.25% L-77 + 5% glycerin 75 86 81 15 MON-O139/Arquad B-100 (2:1) 18 62 40 MON-O139/Arquad B-100 + 0.25% L-77 63 68 66 MON-O139/Arquad B-100 + 0.25% L-77 + 5% glycerin 77 87 82 MON-0139/Arquad B-100 (4:1) 2 53 28 20 MON-0139/Arquad B-100 + 0.25% L-77 82 78 80 MON-O139/Arquad B-100 + 0.25% L-77 + 5% glycerin 62 83 72 MON-O139/Arquad B-100 (8:1) 3 63 33 MON-0139/Arquad B-100 + 0.25% L-77 60 90 75 25 MON-0139/Arquad B-100 + 0.25% L-77 67 78 72 + 5% glycerin -52- 09-21(2873)A EXAMPLE 22 The effect of different surfactant types on the efficacy and rainfastness of glyphosate + L-77 + glycerin tank mixtures on seedling johnsongrass and barnyardgrass. Simulated rainfall equivalent to 6.4 mm of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 0.42 kg ae/ha. Data show average percent growth inhibition at 27 days after treatment.

Treatment Rainfall Seedling johnsongrass Average % Barnyardgrass Inhibition Roundup® None 100 73 6.4 mm 23 30 Roundup® + 0.25% L-77 None 84 65 6.4 mm 0 17 Roundup® + 0.25% L-77 None 99 90 20 + 5% glycerin 6.4 mm 85 89 MON-0139 + 0.09% MON-0818 None 100 94 6.4 mm 40 23 MON-0139 + 0.09% MON-0818 None 68 50 + 0.25% L-77 6.4 mm 3 13 25 MON-0139 + 0.09% MON-0818 None 100 97 + 0.25% L-77 + 5% glycerin 6.4 mm 97 97 -5309-21(2873)A wherein Witconate X-7163 is of the formula CnH2n+iOSO3 wherein n = 8 to 10 Treatment Seedling johnson- BarnyardRainfall grass grass Average % Inhibition MON-0139 + 0.09% Ethoquad None 100 99 C/12 + 0.25% L-77 6.4 mm 100 85 + 5% glycerin MON-0139 + 0.09% Sorpol None 100 87 8227 6.4 mm 17 12 MON-0139 + 0.09% Sorpol None 42 30 8227 -t- 0.25% L-77 6.4 mm 8 3 MON-0139 + 0.09% Sorpol None 93 98 8227 + 0.25% L-77 6.4 mm 91 74 + 5% glycerin MON-0139 + 0.09% Ethomeen None 98 94 C/12 6.4 mm 27 17 MON-0139 + 0.09% Ethomeen None 38 70 C/12 + 0.25% L-77 6.4 mm 13 5 MON-0139 + 0.09% Ethomeen None 100 100 C/12 + 0.25% L-77 6.4 mm 97 85 + 5% glycerin MON-0139 + 0.09% Igepal None 98 88 CA-720 6.4 mm 68 60 MON-0139 + 0.09% Igepal None 12 5 CA-720 + 0.25% L-77 6.4 mm 13 10 MON-0139 + 0.09% Igepal None 100 95 CA-720 + 0.25% L-77 6.4 mm 97 91 + 5% glycerin MON-0139 + 0.09% nonyl- None 100 94 phenol blend 6.4 mm 30 23 MON-0139 + 0.09% nonyl- None 3 12 phenol blend + 0.25% L-77 6.4 mm 18 13 -54- 09-21(2873)A Seedling johnson- BarnyardTreatment Rainfall grass grass Average % Inhibition MON-0139 + 0.09% nonylphenol blend + 0.25% L-77 + 5% glycerin MON-0139 + 0.09% Sterox NJ None 6.4mm None 6.4 mm 100 87 100 0 98 70 91 0 10 MON-0139 + 0.09% Sterox NJ None 28 10 + 0.25% L-77 6.4 mm 0 0 Igepal CA-720 = π (CH2CH2O)12.5h I-8»l 7 Sterox NJ = (CH2CH20)9.5h L9M1 9 u 15 Sorpol 8227 = mix of Cl 2¾ 5 — ch2 ch2 oh 1 + —N—CH3 Cl ch2ch2oh with alkyl phenol ethoxylate 20 CH2CH2OH Ethoquad C/12 is R—N—CH3 Cl where 1 ch2ch2oh R is from coco fatty acid. Ethomeen C/12 is £H2ch2oh R—Νζ^ where xch2 ch2oh R is from coco fatty acid. -55- 09-21(2873)A Seedling johnson- BarnyardTreatment Rainfall grass grass Average % Inhibition MON-0139 + 0.09% Sterox NJ None 100 90 + 0.25% L-77 + 5% glycerin 6.4 mm 90 86 MON-0139 + 0.09% Miranol None 100 99 CM-SFK 6.4 mm 0 13 MON-0139 + 0.09% Miranol None 62 32 10 CM-SFK + 0.25% L-77 6.4 mm 0 0 MON-0139 + 0.09% Miranol None 98 76 CM-SFK + 0.25% L-77 + 5% glycerin 6.4 mm 95 62 MON-0139 + 0.09% Aerosol None 53 27 15 MA-80 6.4 mm 0 0 MON-0139 + 0.09% Aerosol None 20 28 MA-80 + 0.25% L-77 6.4 mm 0 0 MON-0139 + 0.09% Aerosol None 100 88 MA-80 + 0.25% L-77 6.4 mm 100 78 20 + 5% glycerin MON-0139 + 0.09% Frigate None 100 95 6.4 mm 45 43 MON-0139 + 0.09% Frigate None 73 78 + 0.25% L-77 6.4 mm 10 8 25 MON-0139 + 0.09% Frigate None 100 93 + 0.25% L-77 + 5% glycerin 6.4 mm 85 98 O O II II Aerosol MA-80 is ϋθΗι3O-C-CH-CH2-C-O-CgHj3 I S03Na+ Frigate is an adjuvant based on tallow amine ethoxylate -5609-21(2873)A Mirano1 CM-SFK N-CH2 I N+—CH2 I I C2H4OH OH~ where CH2COO'Na+ R is a coco fatty acid or CH2CH2OH II I R-CNH—CH2—CH2—N—CH2 COO'Na+ -57- 09-21(2873)A EXAMPLE 23 The effect of different glyphosate salts on the efficacy and rainfastness of glyphosate + L-77 + glycerin tank mixtures on seedling johnsongrass and barnyardgrass. Simulated rainfall equivalent to 6.4 mm of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 0.42 kg ae/ha. Data show average percent growth inhibition at 27 days after treatment.

Seedling johnson- BarnyardTreatment Rainfall grass grass Average % Inhibition Roundup® None 100 88 6.4 mm 17 25 Roundup® + 0.25% L-77 None 50 33 6.4 mm 8 17 Roundup® + 0.25% L-77 None 100 94 20 + 5% glycerin 6.4 mm 97 87 Sodium glyphosate + 0.09% None 98 80 MON-0818 6.4 mm 4-5 27 Sodium glyphosate + 0.09% None 42 37 MON-0818 + 0.25% L-77 6.4 mm 10 3 25 Sodium glyphosate + 0.09% None 100 92 MON-0818 + 0.25% L-77 6.4 mm 99 80 + 5% glycerin Potassium glyphosate + None 99 83 0.09% MON-0818 6.4 mm 48 28 30 Potassium glyphosate + None 62 55 0.09% MON-0818 + 0.25% L-77 6.4 mm 7 13 Potassium glyphosate + None 100 73 0.09% MON-0818 + 0.25% L-77 6.4 mm 96 90 + 5% glycerin -58- 09-21(2873 )A Seedling johnson- BarnyardTreatment Rainfall grass grass Average % Inhibition Copper glyphosate + 0.09% None 97 70 MON-0818 6.4 mm 3 10 Copper glyphosate + 0.09% None 12 22 MON-0818 + 0.25% L-77 6.4 mm 7 3 Copper glyphosate + 0.09% None 100 72 10 MON-0818 + 0.25% L-77 + 5% glycerin 6.4 mm 96 67 IPA glyphosate + 0.09% None 100 78 MON-0818 6.4 mm 35 48 IPA glyphosate + 0.09% None 58 38 15 MON-0818 + 0.25% L-77 6.4 mm 15 22 IPA glyphosate + 0.09% None 100 88 MON-0818 + 0.25% L-77 + 5% glycerin 6.4 mm 88 80 Ammonium glyphosate + 0.09% None 100 89 20 MON-0818 6.4 mm 32 38 Ammonium glyphosate + 0.09% None 88 81 MON-0818 + 0.25% L-77 6.4 mm 7 23 Ammonium glyphosate + 0.09% None 100 88 25 MON-0818 + 0.25% L-77 +· 5% glycerin 6.4 mm 86 82 -5909-21(2873 )A EXAMPLE 24 The effect of different humectants on the efficacy and rainfastness of glyphosate + L-77 tank mixtures on seedling johnsongrass and barnyardgrass.

Simulated rainfall equivalent to 6.4 mm of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 0.42 kg ae/ha. Data show average percent growth inhibition at 26 days after treatment.

Seedling johnson- BarnyardTreatment Rainfall grass grass_ Average % Inhibition Roundup® None 100 90 15 6.4 mm 50 30 MON-0139 + 0.09% MON-0818 None 100 63 6.4 mm 37 27 MON-0139 + 0.09% MON-0818 None 97 73 20 + 0.25% L-77 6.4 mm 7 17 MON-0139 + 0.09% MON-0818 None 100 89 + 0.25% L-77 + 5% glycerin 6.4 mm 100 81 MON-0139 + 0.09% MON-0818 None 69 50 25 + 0.25% L-77 + 5% dipropylene· glycol 6.4 mm 27 30 MON-0139 + 0.09% MON-0818 None 57 47 + 0.25% L-77 + 5% ethylene glycol 6.4 mm 25 17 ‘ MON-0139 + 0.09% MON-0818 None 96 62 30 + 0.25% L-77 + 5% butanol 6.4 mm 32 30 MON-0139 + 0.09% MON-0818 None 99 98 + 0.25% L-77 + 5% glucose 6.4 mm 93 68 MON-0139 + 0.09% MON-0818 None 100 86 + 0.25% L-77 + 5% fructose 6.4 mm 96 62 MON-0139 + 0.09% MON-0818 None 100 84 35 + 0.25% L-77 + 5% sucrose 6.4 nun 85 67 MON-0139 is an aqueous concentrate comprising the isopropylamine salt of N-phosphonomethylglycine and water, about 62% isopropylamine salt by weight.

MON-0818 is an ethoxylated tallow amine useful as a 40 surfactant. -6009-21(2873)A EXAMPLE 25 Response of seedling johnsongrass, barnyardgrass and velvetleaf to tank mixtures containing ammonium glyphosate and L-77 with low level of glycerin for effi5 cacy and rainfastness. Simulated rainfall equivalent to 6.4 mm of rainfall was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 0.42 kg ae/ha.

Data show average percent growth inhibition at 28 days after treatment.

Seedling johnson- Barnyard- Velvet- Treatment Rainfall grass grass leaf 15 Average ° & Inhibition Roundup® None 100 100 99 6.4 mm 33 38 0 Roundup® + 0.25% L-77 None 25 42 100 6.4 mm 20 23 100 Roundup® + 0.25% L-77 None 47 90 100 20 + 1% glycerin 6.4 nun 60 73 97 Roundup® + 0.25% L-77 None 100 98 100 + 5% glycerin 6.4 mm 100 100 100 Ammonium glyphosate + None 98 100 92 25 0.09% MON-0818 6.4 mm 22 25 0 Ammonium glyphosate + None 35 55 100 0.09% MON-0818 - 0.25% L-77 6.4 mm 13 10 100 Ammonium glyphosate + None 87 92 100 0.09% Mon-0818 + 0.25% 6.4 mm 33 58 100 30 L-77 + 1% glycerin Ammonium glyphosate + None 100 100 100 0.09% Mon-0818 + 0.25% L-77 + 5% glycerin 6.4 mm 100 100 87 Ammonium glyphosate + None 100 100 72 35 0.09% Ethoquad C/12 6.4 mm 17 17 0 Ammonium glyphosate + None 30 48 100 0.09% Ethoquad C/12 + 0.25% L-77 6.4 mm 32 22 88 Ammonium glyphosate + None 65 95 100 40 0.09% Ethoquad C/12 + 0.25% L-77 + 1% glycerin 6.4 mm 15 18 100 Ammonium glyphosate + None 100 100 100 0.09% Ethoquad C/12 + 0.25% L-77 + 5% glycerin 6.4 mm 97 92 75 -61- 09-21(2873)A EXAMPLE 26 Response of certain broadleaf weeds to postemergence treatments of herbicide tank mixtures containing acifluorfen (Blazer® herbicide) + L-77 + glycerin.

Data show average percent growth inhibition at 21 days after treatment.

Herbicide Rate Cockle Morning Velvet Hemp Treatment kg ai/ha bur glory leaf Sesbania Blazer herbicide 0.14 0.42 0 3 0 0 0 0 20 33 Blazer + 0.5% Triton 0.14 2 0 0 47 AG-9 8 0.42 17 3 10 97 Blazer + 0.5% Triton 0.14 25 55 20 47 15 AG-98 + 0.5% L-77 0.42 37 67 27 100 Blazer + 0.5% Triton 0.14 17 47 27 72 AG-98 + 0.5% L-77 + 10% glycerin 0.42 37 100 88 97 Blazer + 0.5% L-77 0.14 10 33 20 28 20 0.42 25 68 87 100 Blazer + 0.5% L-77 0.14 17 0 33 27 + 10% glycerin 0.42 80 98 80 77 Blazer + 0.5% X-45* 0.14 20 23 20 57 + 10% glycerin 0.42 20 43 48 100 25 Blazer + 0.5% X-45 0.14 7 20 17 48 + 0.5% L-77 + 10% glycerin 0.42 18 78 63 97 Blazer + 0.5% Triton 0.14 5 3 0 32 30 AG-98 + 0.5% Igepal 0.42 CA-210 + 10% glycerin 17 12 32 53 Blazer + 0.5% L-77 0.14 30 27 23 37 + 0.5% Igepal CA-630 0.42 48 87 53 100 + 10% glycerin * X-45, Blazer + humectant only Triton Triton Igepal Igepal -62- 09-21(2873)A AG-98 = Tank mix adjuvant, 80% alkylaryl polyoxyethylene glycols X-45 = C8H17-0-(CH2CH2O)5H CA-630 = C8H17-0-(CH2CH2O)9H CA-210 = C8H17-0-(CH2CH2O)i . SH -63- 09-21(2873)A EXAMPLE 27 Response of seedling johnsongrass and barnyardgrass to postemergence treatments of herbicide tank mixtures containing imazaquin (Scepter® herbicide) L-77 + glycerin. Scepter was applied at ai/ha. Data show average percent growth 0.42 kg inhibition active at 21 days after treatment, ingredient). (a.i. means 10 Treatment Seedling johnsongrass Barnyard qrass Scepter herbicide 27 27 Scepter + L-77 47 50 Scepter + L-77 + glycerin 57 53 Scepter + Triton X-45 + glycerin 63 47 -64- 09-21(2873)A EXAMPLE 28 Response of barnyardgrass to tank mixtures containing Roundup®, Silicone Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Roundup® was applied at 0.42 kg ae/ha, Fluid at 0.25% (v/v), and glycerin at 2.5% (v/v). The spray volume was equivalent to 187 liters per hectare of spray solution.

Average % Inhibition (25 DAT) 0 Rain 6.4 mm Rain Treatment -glycerin +glycerin -glycerin +glycerin Roundup® 95 100 12 8 Roundup® + Fluid 3 20 87 0 57 Roundup® + Fluid 7 40 100 0 72 Roundup® + Fluid 8 40 99 2 68 Roundup® + Fluid 4 100 99 3 73 Roundup® + Fluid 6 100 100 30 72 Roundup® + Fluid 10 100 100 5 64 where fluids are defined hereinafter and are useful as 20 silicone surfactants herein. - means without + means with -65- 09-21(2873)A EXAMPLE 29 Response of barnyardgrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 27 days after treatment. Roundup® was applied at 0.42 kg ae/ha, Fluid at 0.25% (v/v), and glycerin at 5% (v/v). The spray volume was equivalent to 187 liters per hectare of spray solution.

Average % Inhibition (25 DAT) Rain 6.4 mm Rain Treatment -glycerin +glycerin -glycerin +glycerin Roundup® 100 99 27 27 Roundup® + Fluid 1 100 100 50 98 Roundup® + Fluid 5 100 100 5 100 -66- 09-21(2873)A EXAMPLE 30 Response of barnyardgrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Roundup® was applied at 0.42 kg ae/ha, Fluid at 0.5% (v/v), and glycerin at 5% (v/v). The spray volume was equivalent to 187 liters per hectare of spray solution.

Treatment Average ° 0 Rain ί Inhibition 6.4 (25 DAT) mm Rain Roundup® 96 3 Roundup® + glycerin 94 3 Roundup® + Fluid 9 86 0 Roundup® + Fluid 9 + glycerin 100 85 -6709-21(2873)A EXAMPLE 31 Response of barnyardgrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 24 days after treatment. Roundup® was applied at 56 kg ae/ha, Fluid at 1% (v/v). The spray volume was equivalent to 187 liters per hectare.

Treatment Roundup® Roundup® + Fluid 6 Roundup® + Fluid 6+1% 15 glycerin Roundup® + Fluid 6+3% glycerin Roundup® + Fluid 6+5% glycerin Average % Inhibition (25 DAT) 0 Rain 6.4 mm 100 23 100 63 100 53 100 86 100 95 -6809-21(2873)A EXAMPLE 32 Response of barnyardgrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 26 days after treatment. Roundup® was applied at 0.42 kg ae/ha, Fluid at 0.25% (v/v). The spray volume was equivalent to 187 liters per hectare.

Treatment Roundup® Average % Inhibition (25 DAT) 0 Rain 6.4 mm Rain Roundup® + Fluid 2 Roundup® glycerin + Fluid 2 + 1% Roundup® glycerin + Fluid 2 + 2.5% Roundup® + Fluid 2 + 5% glycerin Roundup + 5% glycerin 98 3 73 3 98 40 86 63 88 98 85 3 -69- 09-21(2873 )A EXAMPLE 33 Response of rhizome johnsongrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 23 days after treatment. Roundup® was applied at 0.42 kg ae/ha, and glycerin at 1% (v/v). The spray volume was equivalent to 187 liters per hectare. Average % Inhibition (25 DAT) Treatment 0 Rain 6.4 mm Rain Roundup® 53 8 Roundup® + + glycerin 0.125% Fluid 6 100 73 Roundup® + + glycerin 0.25% Fluid 6 100 100 Roundup® + + glycerin 1% Fluid 6 100 93 Roundup® + 1% Fluid 6 99 76 ΪΕ 893949 -70- 09-21(2873)Α EXAMPLE 34 Response of rhizome johnsongrass to tank mixtures containing Roundup®, Fluids and glycerin in the absence or presence of 6.4 mm simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 22 days after treatment. Roundup® was applied at 0.56 kg ae/ha and Fluids 0.5% (v/v). The spray volume was equivalent to 187 liters per hectare of spray solution.

Silicone Additive Glycerin Con. Average % Inhibition (25 DAT) 6.4 mm Rain (%) 0 Rain NONE 95 27 Fluid 11 0 52 68 0.5 80 43 15 1 48 58 2 76 67 5 100 89 Fluid 7 0 13 5 0.5 65 15 20 1 98 43 2 98 77 Fldid 8 0 18 7 0.5 45 20 1 72 45 25 2 99 78 Fluid 6 0 90 73 0.5 99 88 1 99 91 2 100 98 30 Fluid 10 0 92 60 0.5 96 80 1 99 93 2 99 97 NOTE: 35 Glycerin concentration is expressed at % of the total spray volume based on a spray gallonage equivalent to 187 liters per hectare.

Fluid 11 is a material of Formula IV wherein Q and R are both methyl, x and y are both zero, G is -CH2CH2CH2(OCH2CH2)7OMe and z is 1. -71- 09-21(2873)A FLUIDS Me3SiO(SiMe2O)x(SiMeAO)y(SiMeGO)zSiMe3 FLUID ALKANE CHAIN LENGTH ALKANE UNITS (y) EO UNITS (m) GLYCOL UNITS (2) DIMETHYL UNITS (X) 1 16 0.90 12 4.60 8.5 2 12 1.32 12 2.68 2.0 3 12 0.50 4 5.00 8.5 4 12 1.50 24 2.50 2.0 10 5 12 0.64 7 1.36 0.0 6 12 0.64 24 1.36 0.0 7 12 0.50 4 3.50 2.0 8 12 0.25 4 1.75 0.0 9 12 2.00 12 9.00 19.0 15 10 12 1.00 24 4.50 8.5 all wherein G is the glycol moiety of -CH2CH2CH2(OCH2CH2)mOMe

Claims (55)

WHAT IS CLAIMED IS:

1. An enhanced herbicidal composition comprising a herbicidally effective amount of a herbicide, humectant, and silicone surfactant. 5

2. The herbicide composition of Claim 1 wherein said herbicide is selected from the group consisting of aciflourfen, 5-(2-chloro-a,a,or,-trifluoro-p-tolyloxy)-2-nitrobenzoic acid and agriculturally acceptable salts thereof; oxyfluorfen, 10 2-chloro-l-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene; lactofen, 1-(carboethoxy)ethyl 5—[2 — chloro-4-(trifluoromethyl) phenoxyl]-2-nitrobenzoate; imazaquin, 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)5-oxo-lH-imidazol-2-yl]-3-quinoline carboxylic acid 15 and agriculturally acceptable salts thereof; N-phosphonemethylglycine and/or agriculturally acceptable salts thereof, mixtures thereof and the like.

3. The herbicide composition of Claim 2, wherein said herbicide is N-phosphonomethylglycine or 20 an agriculturally acceptable salt thereof.

4. The herbicide compostion of Claim 3, wherein said agriculturally acceptable salt of N-phosphonomethylglycine is the isopropylamine salt.

5. The herbicide composition of Claim 3, 25 which comprises the isopropylamine salt of N-phosphonomethylglycine, Silwet L-77, and humectant. -73- 09-21(2873)A

6. The herbicidal composition of Claim 1 wherein said silicone surfactant comprises a polyalkylene oxide modified dimethylpolysiloxanes (C 2 H 4 O) a (C 3 H 6 ) b 2 15 wherein a ranges from 3 to about 24, b ranges from 0 to about 15, x is in the range from about 0 to 3 and y ranges from 1 to 5 and in which Z can be hydrogen or a lower alkyl radical having 1-3 carbon atoms or an acyl group having 2 to 4 carbon atoms. 20

7. The herbicidal composition of Claim 6, wherein a ranges from 4 to 7, b ranges from 0 to 3, x = 0 and y = 1.

8. The herbicidal composition in Claim 1, wherein said silicone surfactant is a compound of the 25 Formula R R I I QR 2 SiO(SiR 2 O) (SiO) (SiO) SiR 2 Q x , y , Z 30 AG wherein R is independently selected from alkyl radicals having 1 to 6 carbon atoms; A is a linear or branched alkyl radical having 7 to 30 carbon atoms; G is a glycol moiety having the formula -R' 35 (OCH 2 CH 2 ) m OZ, in which R’ is a divalent alkylene group having 1 to 6 carbon atoms, Z is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 -74- 09-21(2873)A to 4 carbon atoms and m is 8 to about 100; Q is independently selected from the group consisting of said radical A, said glycol moiety G and said radical R; x is 0 to 100, y is 0.1 to 25 and z is 0.1 to 50. 5

9. The herbicidal composition of Claim 8, wherein said silicone surfactant is a compound of the average Formula Me Me 1 . 1 . 10 Me 3 SiO(SiO) 0 .64(SiO) x . 36 SiMe 3 l—CH 2 CH 2 CH 2 (OCH 2 CH 2 ) 2 4 oc (O ) ch 3 L(ch 2 ) 11 ch 3 15 wherein Me denotes a methyl radical.

10. The composition of Claim 1, wherein said herbicide is N-phosphonomethylglycine or an agriculturally acceptable salt thereof and said silicone surfactant is selected from the group 20 consisting of those having the average formula Me MeSiO(SiO)SiMe 3 I 25 C 3 H 6 -O(C 2 H 4 O) a (C 3 H 6 O) b Z wherein Me is a methyl radical, a is from 4 to 7, b is 0 to 3 and Z is selected from the group of hydrogen, alkyl radical having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms and those 30 having the average formula R R I I Q(R 2 )SiO(SiR 2 O) (SiO)(SiO) SiR 2 Q X I y , z 35 AG -75- 09-21(2873)A wherein R is independently selected from alkyl radicals having 1 to 6 carbon atoms; A is a linear or branched alkyl radical having 7 to 30 carbon atoms; G is a glycol moiety having the formula 5 -R’(OCH 2 CH 2 ) m °Z, in which R’ is a divalent alkylene group having 1 to 6 carbon atoms, Z is selected from the group consisting of hydrogen, an alkyl radical having 1 to 3 carbon atoms and an acyl group having 2 to 4 carbon atoms and m is 8 to about 100; Q is 10 independently selected from the group consisting of said radical A, said glycol moiety G and said alkyl radical R; x is 0 to 100, y is 0.1 to 25 and z is 0.1 to 50 .

11. The herbicidal composition of Claim 15 10, wherein said silicone surfactant comprises those having the average formula Me I Me 3 SiO(SiO)SiMe 3 20 | C 3 H 6 -O(C 2 H 4 O) a (C 3 H 6 O) b Z wherein Me is a methyl radical, a is from 4 to 7, b is 0 to 3 and Z is selected from the group of hydrogen, alkyl radical having 1 to 3 carbon atoms or 25 an acyl group having 2 to 4 carbon atoms.

12. The herbicidal composition of Claim 10, wherein said agriculturally acceptable salt of N-phosphonomethylglycine is an amine, trimethylsulfonium, or an iminourea salt. 30

13. The herbicidal composition of Claim 10, wherein said agriculturally acceptable salt of N-phosphonomethylglycine is the isopropylamine salt. -76- 09—21(2873)A

14. The herbicidal composition of Claim 7, wherein said humectant is selected from the group consisting of sorbitol, glycerol, polyethylene glycol, polypropylene glycol, propylene glycol, 5 triethylene glycol, glycerine, sodium stearate, microcrystalline cellulose, homolinear polymers of ethylene oxide, soluable collagen, lactic acid and salts thereof, cane molasses and the like.

15. The herbicidal composition of Claim 7, 10 wherein the concentration of active ingredient is in the range from about 2 to about 70% by weight.

16. The herbicidal composition of Claim 12, wherein the concentration of said active ingredient is in the range from about 4 to about 40% 15 by weight.

17. The herbicidal composition of Claim 13, wherein in a final application solution, the concentration of said active ingredient is in the range from about 0.05% to about 20% by weight. 20

18. The composition of Claim 14, wherein in a final application solution to be made on foliage, the concentration of said active ingredient is in the range from about 0.15% to about 5% by weight. 25

19. The composition of Claim 14, wherein the ratio of active ingredient to silicone surfactant is about 1:1.

20. The composition of Claim 16, wherein the ratio of active ingredient to silicone surfactant 30 is in the range from about 1:30 to about 50:1. . -77- 09-21(2873 )A

21. The composition of Claim 17, wherein the weight ratio of active ingredient to silicone surfactant is in the range from about 1:15 to about 10:1. 5

22. The composition of Claim 16, wherein the ratio of silicone surfactant to humectant is about the same.

23. The composition of Claim 19, wherein the weight ratio of silicone surfactant to humectant 10 is in the range from about 1:1 to about 1:200.

24. The composition of Claim 20, wherein the weight ratio of silicone surfactant to humectant is in the range from about 1:5 to about 1:50.

25. The composition of Claim 19, wherein 15 the weight ratio of active ingredient to adjuvant is in the range from about 1:5 to about 10:1.

26. The composition of Claim 22, wherein the weight ratio of active ingredient to adjuvant is in the range from about 1:2 to about 4:1. 20

27. A composition of Claim 1, which further comprises inert adjuvants and water.

28. The composition of Claim 1, wherein said composition is a dry composition.

29. A herbicidal method of use for killing 25 or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 1. -78- 09-21(2873)A

30. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

2. Claim 2. 5 31. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 3.

32. A herbicidal method of use for killing 10 or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 4.

33. A herbicidal method of use for killing or controlling weeds which comprises contacting a 15 plant with an effective amount of the composition of Claim 5.

34. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of 20 Claim 6.

35. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 7. 25 36. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

Claim 8. -79- 09-21(2873)A

37. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

Claim 9. 5 38. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 10.

39. A herbicidal method of use for killing 10 or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 11.

40. A herbicidal method of use for killing or controlling weeds which comprises contacting a 15 plant with an effective amount of the composition of Claim 12.

41. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of 20 Claim 13.

42. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 14. 25 43. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

Claim 15. -80- 09-21(2873)A

44. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

Claim 16. 5 45. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 17.

46. A herbicidal method of use for killing 10 or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 18.

47. A herbicidal method of use for killing or controlling weeds which comprises contacting a 15 plant with an effective amount of the composition of Claim 19.

48. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of 20 Claim 20.

49. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 21. 25 50. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of

Claim 22. -81- 09-21(2873)A

51. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 23.

52. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 24.

53. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 25.

54. A herbicidal method of use for killing or controlling weeds substantially as hereinbefore described by way of Example.

55. A herbicidal composition substantially as hereinbefore described by way of Example.