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Improved herbicide formulations container silicone surfactant and their uses
AU609628B2
Australia
- Inventor
David Zachary Becher Joseph Allen Bohn Miguel Molina Dayawon Victor George Difate Robert Alan Ekeland Lenin James Petroff Sudabathula Rajaramamohana Rao David Joseph Romenesko Joseph Jude Sandbrink Stephen Michael Striebel - Current Assignee
- Monsanto Co
Worldwide applications
Application AU38389/89A events
1989-06-13
1990-01-12
1991-05-02
Application granted
1991-05-02
2009-06-13
Anticipated expiration
Status
Ceased
Description
translated from
ii I COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 FORM Application Number: Class: Int. Class Complete specification: Lodged: Accepted: Published: Priority: Related Art: Name of Applicant: Address of Applicant: Actual Inventor/s: Address for Service: MONSANTO COMPANY 800 North Lindbergh Boulevard, St. Louis Missouri, 63167, United States of America.
MIGUEL MOLINA DAYAWON; DAVID ZACHARY BECHER; SUDABATHULA RAJARAMAMOHANA RAO; JOSEPH JUDE SANDBRINK; JOSEPH ALLEN BOHN; STEPHEN MICHAEL STRIEBEL; LENIN JAMES PETROFF; ROBERT ALAN EKELAND; DAVID JOSEPH ROMENESKO; and VICTOR GEORGE DI FATE, JR.
E. F. WELLINGTON CO., Patent and Trade Mark Attorneys, 312 St. Kilda Road, Melbourne, 3004, Victoria.
Complete Specification for the invention entitled: "IMPROVED HERBICIDE FORMULATIONS AND THEIR USE" The following statement is a full description of this invention including the best method of performing it known to us.
1 -lA- 09-21(2873)A
BACKGROUND
This invention relates to a method and composition for enhancing the efficacy of herbicides in particular herbicides selected from the group consisting of acifluorfen, its agriculturally accept- 5 able salts, o::yfluorfen, lactofen, imazaquin acid and the agriculturally acceptable salts thereof, N-phosphonomethylglycine and its agricultirally acceptable salts thereof, mixtures thereof and the like.
10 This invention also relates to a ready to Suse composition comprising an enhanced delivery system for herbicides.
Herbicides may be applied to plants in a S"variety of methods including different formulations.
15 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 climatology of the area at the time of treatment.
VVW
A 7 0 WO 89/12394 PCT/US89/02570 -2- In many areas of the world, it is highly desirable to apply a herbicide composition having rainfastness quality (adherence to foliage) in areas of high rainfall amounts or under conditions and timing where rainfall is highly likely following application of a herbicide. Further in some areas, it may be particularly desirable to apply herbicide compositions (typically a herbicidal composition) to vegetation which has a thick cuticle and therefore herbicide penetration may be somewhat inhibited.
Use of compositions of this invention produced increased herbicide efficacy particularly in applications of a herbicide in accordance with this invention on rhizome johnsongrass, a narrowleaf perennial, and seedling johnsongrass, barnyardgrass and downy brome which are narrlowleaf annuals.
Glyphosate (N-phosphonomethylglycine) 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 to John E.
Franz 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 to George B. Large on March 15, 1983 discloses trimethylsulfonium and trimethylsulfoxonium salts of N-phosphonomethylglycine
B
WO 89/12394 PCT/US89/0257 -3and their use as herbicides and herbicidal compositions. Iminourea and substituted iminourea salts such as guanidine and aminoguanidine 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.
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 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 and propylene glycol, and polyhdric alcohols in mixtures with free fatty acids and DMSO. 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 HVdrocarbon 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 discloses use of a nonionic silicone surfactant, L-77 (organosilicone block copolymer Union Carbide New York, the nonionic hydrocarbon surfactant and 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.
g c WO 89/12394 PCT/US89/02570 -4- Monsanto 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 also containing an ethoxylated -nine surfactant, inert adjuvants and water.
The use of an organosilicone surfactant, such as Silwet L-77 in tank mixes with commercially purchased Roundup® herbicide at time 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 composition containing Silwet L-77 (without added humectant) has been applied to many plants, particularly on narrowleaf species.
Monsanto sells "Pulse" penetrant (which is L-77) for use with Roundup herbicide and discloses on the Pulse label that the addition of Pulse can reduce the 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.
Stauffer Australian Patent Application AU-A-64552/86 published May 7, 1987 discloses herbicide compositions comprising an herbicidally effective amount of an agriculturally acceptable salt of N-phosphonomethylglycine, at least one humectant having a moisture capacity -ubstantially equivalent to that of sorbitol; inert adjuvants; and water; wherein the ratio of to ranges from about 1:33 to about 5:1 by weight. A herbicidal method of use of such compositions is also disclosed.
WO 89/12394 PCT/US89/0257t Further, at page 3, this published patent application 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.
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, whereas cationic amino silicone surfactants enhanced to a lesser extent.
Great Britain Patent Number 1,225,249 to Dow Corning Corporation, published December 1, 1971, discloses herbicide compositions 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-inc_ asing adjuvants ~e WO 89/12394 PCT/US89/02570 -6discussed 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.
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-phosphonomethylglycine 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 composition 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.
7 09-21(2873)A It is yet another object of the invention to provide a delivery systeii 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, on the plant foliage.
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 present invention provides in a first aspect an enhanced herbicidal composition comprising a herbicidally S effective amount of a herbicide, humectant, and silicone surfactant.
The present invention provides in a second aspect a herbicidal method of killing or controlling weeds which 20 comprises contacting a plant with an effective amount of a composition of the present invention.
Thus, the above and other objects are met in this invention which provides a novel method and composition for enhancing the efficacy of herbicides, in particular foliar applied herbicides more particularly herbicides selected from the group consisting of acifluorfen (5-(2-chloro-aaa-trifiuorop-tolyloxy)--2-nitrobenzoic acid and its agriculturally acceptable salts thereof, oxyfluorfen(2-chloro-l-(3-ethoxy-4nitrophenoxy)-4-(trifluoromethyl)benzene; lactofen, (Carboethoxy)ethyl 5-'2-chloro-4-(trifluoromethyl) phenoxyl'-2nitrobenzoate; imazaquin (2-'4,5-Dihydro-4-methyl-4- (l-methylethyl)-5-oxo-lH-imidazol-2--yl'3-quinolinecarboxylic acid and the agriculturally acceptable salts thereof, N-phosphonomethylglycine or an agriculturally acceptable salt thereof, derivatives thereof, mixtures thereof and the like.
g- 09-21(2873)A DETAILED DESCRIPTION OF THE INVENTION 0 0 0 so 0.0.
0 0 e
S.
S
S
a 0 0*
C
e 0* S *0 S o The invention herein comprises a herbicidal composition comprising a herbicidally effective amount of a herbicide in particular a herbicide selected from the group consisting of acifluorfen (5-(2-chloro-aaatrifluoro-p-tolyloxy)-2-nitrobenzoic acid and its agriculturally acceptable salts thereof, (see US Patent 3,979,437); oxyfluorfen (2-chlo- ro-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-2yl']-3-quinolinecarboxylic acid and the agriculturally acceptable salts thereof, N-phosphonomethylglycine or 15 an agriculturally acceptable salt thereof, mixtures thereof and the like, humectant, and silicone surfactant, optionally with inert adjuvant(s) and water.
Herbicide compositions herein include bch package and tank mix compositions. The term agriculturally acceptable as employed herein includes agricultural, 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-s-triazine, 2-chloro-4,6-bis(isopropylamino)-s-triazine; 2-chloro-4,6-bis(ethylamine)-s-triazine; 3-isopropyl-lH-2,1, 3-benzothiadiazin-4-(3H)-one 2,2-dioxide, 3-amino- 1,2,4-triazole; 5-bromo-3-isopropyl-6-methyluracil;
A"
0,.
IT
o^i 2-(4-isopropyl-4-methyl-5-oxo-2-imdazolin-.1-yl-)3guinolinecarboxylic 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-4-methyl- 5-oxo-2-imidazolin-2-yl )-p-toluate; and further including acids/esters/alcohols such as (2, 2-dichloropropionic acid; 2-methyl-4-chlcropheno xyacetic acid, 2,4-dichlorophenoxyacetic acid, metbyl-2- [4-(2,4-dichlorophenoxy)phenoxyjpropionate, 3-ainino-2 ,5-dichlorobenzoic acid, 2-methoxy-3 ,6dichlorobenzoic acid, 2,3, 6-trichlorophenylacetic acid, N-l-naphthylphthalamic acid, sodium 5-[2-chloro- 4- (trifluoromethyl )phenoxyj -2-nitrobenzoate, 4, 6-dinitro-o-sec-butylphenol, butyl [(trifluoromethyl -pyridinyl )oxy] -phenoxyl -propanoate; and cyclohexanediones such as sethoxydium, and garlon and ethers such as 2,4-dichlorophenyl-4-nitrophenyl ether, 2 -chloro-trifuluorop-tolyl-3-ethoxy-4-nitrodiphenyl ether, 5-(2-chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl 2-nitro-benzamide, 1 '-(carboethoxy) ethyl [2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate and other diphenylethers and other miscellaneous herbicides such as 2,6-dichlorobenzonitrile, monosodium. acid methanearsonate, disodium. methanearsonate, 2-(2-chlorophenyl)methyl-4,4-dimethyl-3isoxazolidinone.
Other herbicides useful for practicing the invention herein include fosamine, haloxyfop, imazapyr, mefluidide, metsulfuron, picloram, quizalofop and imidazolinones.
The above compounds are intended merely as representative of the types of compounds which may be employed in this invention. N-phosphonomethylglycine PCT/US89/0257O WO 89/12394 itself may be employed in this invention or optionally any agriculturally acceptable salt, amide, ester, or derivative thereof, mixtures of one or more agriculturally acceptable derivatives or salts or mixtures of an agriculturally acceptable salt and N-phosphonomethylglycine may be employed.
Typical agriculturally acceptable salts which may be employed include those disclosed in US Patents 3,799,758; 4, 405,531; 4,315,765. Preferred salts include the isopropylamine, sodium, ammonium, trimethylsulfoniunL 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 poly-propylene glycol, propylene glycol, tri tthylene glycol, glycerin, sodium stearate, microcrystalline cellulose, homolinear polymers of ethylene oxide and soluble collagen, sold under the tradename 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 91 I -11- 09-21(2873)A e%
*I
'bO 1.
et *-i
I
(water-hating) segments. These products have the general formula: CH CH
CH
3
CH
3 H I Si--CH 3
(I)
Si.- S CHE x C3H6 CH3 0
(C
2
H
4 0)a(C3H6O)bZ 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 15 ranges from 1 to J and in which 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 Siliconei 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.
25 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-7507, 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 are particularly described in U.S. Patent 3,299,112 issued to Donald L.
iA 0<
I
WO 89/1,2394 PCT/US89/02570 -12- 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 Me 3 SiO[MeO(C 2
H
4 0) 7
C
3
H
6 SiMeO]SiMe 3 Also useful herein as a silicone surfactant is a silicone glycol of the average structure Me
I
Me 3 SiO(SiO)SiMe 3
(II)
1
R(OCH
2
CH
2
OZ
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 carbon 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 bissiloxane structure having a hydrogen attached to the central silicon atom, said structure being Me Me 3 SiO(SiO)SiMe 3
(III)
H
Generally, the coupling is accomplished in the presence of a platinum catalyst. The skilled artisan will recognize that, in such coupling reactions, a
I
C WO 89/,12394 PCT/LS89/02570 -13fraction of the allyl-termin.ated 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 present invention. These compounds may be represented by the average formula R R I I
QR
2 SiO(SiR 2 0)x (Si) (SiO) SiRzQ (IV) 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 A highly preferred silicone glycol-silicone alkane terpolymer (II) useful in the present invention as a silicone surfactant has the average structure r e WO 89/12394 PCT/US89/02570 -14- Me Me Me 3 SiO(SiO)o.
64 (SiO).e 36 SiMe 3 -CH2CH 2
CH
2 (OCH2CH2) 24 0C(O)CH 3
(V)
-(CH2)11CH 3 wherein Me hereinafter 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 are coupled to an SiH-functional siloxane having the average structure
R
I
Q'R
2 SiO(SiR 2 0)x(SiRO)y zSiR2Q' (VI)
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 moles of alpha-dodecene and 1.90 moles of an allylterminated glycol having the formula CH2=CHCH 2
(OCH
2
CH
2 24 0C(O)CH 3 are reacted with one mole of an SiH-functional siloxane having the average structure Me
I
Me 3 SiO(SiO) 2 .ooSiMe 3
(VII)
I
H
treatment.
WO 89/12394 PCT/US89/02570 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 0 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 as E-Z 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 Preferably, from 0.5 to about 5 parts by weight of (II) are employed for each part of the pesticide 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.
I ju u. ratent 4,j n, o3 i ssuea to ueorge b. Large on March 15, 1983 discloses trimethylsulfonium and trimethylsulfoxonium salts of N-phosphonomethylglycine WO 89/12394 PCT/US89/02570 -16- 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 by weight.
Thereafter in any order one mixes suitable amounts humectant silicone surfactant and optionally inert adjuvant and adds any diluent water.
If desired, one may prepare the composition of this invention by starting with either a herbicide or an agriculturally acceptable salt thereof, or adjuvant, or humectant, or silicone surfactant. Water may be employed if desired in an amount desired.
While the ratios of concentrations of the various components of this invention are hereinafter suggested, those of skill 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 Singredient wil. be in the range from about 2 to about 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 and L-77 in this article.
I I WO 89/12394 PCT/US89/02570 -17about 0.05% to about 20% by weight and preferably in the range from about 0.15% zo 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 active and/or to improve rainfastness.
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.
equivalent to that of sorbitol; inert adjuvants; and water; wherein the ratio of to ranges from about 1:33 to about 5:1 by weight. A herbicidal method of use of such compositions is also disclosed.
WO 89/12394 PCT/US89/02570 -18- 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 of skill 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 adjuvant or conditioning agent), one or more surfaceactive 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 amides, 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 anyhydrides In addition to the herbicidal enhancement provided by the activity-inceasing adjuvants WO 89/12394 PCT/US89/025 -19- (sorbitan) Preferred dispersants are methylcellulose, polyvinylalcohol sodium lignin sulfonates, polymeric alky naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnahp- thalenesulfonates and sodium N-methyl-N-long chain acid laurates.
Suitable surfactants (adjuvants) are disclosed in U.S. Patent 3,799,758 and 4,405,531 supra both of which are incorporated herein in their entirety by 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 use of this invention comprises use of that composition as a post emergent herbicide to kill or control rhizone johnsongrass, seedling johnsongrass, barnyard grass 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 kaolinites, attapulgite clay and synthetic magnesium silicate. The water dispersible powder of this invention usually contain from about 5 to about 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 from about 4.5 to about 94.5 parts by weight of inert solid extender, all parts being by weight of the total composition. Where required, from -e i active ingrealen- -nan wnen a s±±±iouue u.sL.~au.L L present in the formulation.
WO 89/12394 PCT/US89/0250 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 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 composition of this invention can also contain other additaments, for example fertilizers, phytotoxicants and plant growth 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 material fertilizers, phytLtoxicants and applied in a single application. Chemicals useful in combination with the active ingredients of this invention either simultaneously or sequentially including 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, further for example effective amounts of N-phosphonomethylglycine or agriculturally acceptable salts thereof or derivatives c~ (i-metnyletnyi)--oxo-lH-imidazo±-Z--yl' -quino±inecaLoxy.u acid and the agriculturally acceptable salts thereof, N-phosphonomethylglycine or an agriculturally acceptable salt thereof, derivatives thereof, mixtures thereof and the like.
R,,
-7 -1- SWO 89/12394 PCT/US89/02570 -21are 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 composition can also be applied aerially as spray if desired.
The application of an effective amount of the herbicide composition of this invention to selected locus such as a plant foliage is essential for the practice of this invention. The amount of erbicide active ingredient to be employed is depend- 2nt upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, the amount of rainfall as well as the specifi- 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.
2-chloro-4,6-bis(isopropylamino -s-rlazZ.lt; z-u-uro-4,6-bis(ethylamine)-s-triazine; 3-isopropyl-1H-2,1, 3-benzothiadiazin-4-(3H)-one 2,2-dioxide, 3-amino- 1,2,4-triazole; 5-bromo-3-isopropyl-6-methyluracil;
V
i- 's 0' WO 89/12394 PCT/US89/02570 -22- GENERAL PROCEDURE FOR EXAMPLES 1-34 The following weed species were used as indicator weeds: Common Name Seedling johnsongrass Rhizome johnsongrass Downy Brome Barnyardgrass Velvetleaf Yellow nutsedge Crabgrass Cocklebur Redroot Pigweed Scientific Name Sorghum halepense Sorghum halepense Bromus tectorum Echinochloa crus-galli Abutilon theophrasti Cyperus esculentus Digitarias sp.
Xanthium pennsylvanicum Amaranthus retroflexus The narrowleaf and broadleaf test weeds were seeded separately into plastic pots 4 inches in diameter and 3 inches 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 180 Degrees Fahrenheit. 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.
Seedling johnsongrass, barnyardgrass, downy brome, velvetleaf, crabgrass, cocklebur and redroot pigweed were started from seeds, rhizome johnsongrass W i12 9 IS...
WO 89/12394 PCT/ S89/02570 -23plants 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 asorbent mats for sub-irrigation. The greenhouse temperature was maintained at 86 Degrees Fahrenheit during the day and 70 Degrees Fahrenheit 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 4 to 16 inches tall while the broadleaf weeds were 1 to 4 inches 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 20 gallons per acre of spray solution at a spraying pressure of about 30 psi.
The chemical compositions illustrative of compositions of this invention used in the tests were WO 89/12394 PCT/US89/02570 -24formulated as tank mixtures the same day of application. The formulations comprised an agriculturally acceptable salt of N-phosphonomethylglycine namely the isopropylamine salt, an inert adjuvant as a surfactant, a humectant, an organosilicone surface active copolymer and water.
Rates of application based on N-phosphonomethyglycine ranged from about 1/8 to about 3 pounds glyphosate acid equivalent per acre. 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, silicon 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 1/4 inch of simulated rainfall within a period of abou' 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 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 on the effects of the treatments were taken within 7 to 10 days for early 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 X o a mu Y-3Do3 mixtures tnereot and the like.
Compounds of Formula are particularly described in U.S. Patent 3,299,112 issued to Donald L.
SWO 89/12394 PCT/US89/02570 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 is comparative data cbtained therewith in various columns and lines for compositions typical of prior art tank mixes comprising Roundup® herbicide with 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).
_L
WO 89/12394 PCT/US89/02570 -26- 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. Data show average percent growth inhibition at 14 and 28 days after treatment.
Treatment Roundup Rate (lb ae/A) 0.25 0.75 Mean 14 Days After Treatment 14 Days After Treatment Roundup Roundup 1% L-77 No Rainfall 1/4" Rainfall Light Mist No Rainfall 1/4" Rainfall Light Mist No Rainfall 1/4" Rainfall Light Mist No Rainfall 1/4" Rainfall Light Mist 28 Days After Treatment Roundup Roundup 1% L-77
L'
I
WO 89/ f2394 PCT/US89/02570 -27- EXAMPLE 2 Response of rhizeme 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.
Roundup Rate (Ib ae/A) 0.25 0.5 0.75 Treatment Mean 82 Roundup Roundup 1% L-77 Roundup 1% L-77 1% Glycerin 43 Roundup 1% L-77 3% Glycerin Roundup 1% L-77 5% Glycerin 72 Roundup 1% Glycerin Roundup 3% Glycerin Roundup 5% Glycerin r I I II I WO 89/12394 PCT/US89/02570 -28- EXAMPLE 3 Response of seedling johnsongrass to Roundup and tank mixtures containing Roundup L-77 and Roundup L-77 Glycerin at different Glycerin concentration in the spray mixture with and without simulated rainfall treatment. Simulated rainfall equivalent to 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. All treatments contained Roundup at 1/2 lb ae/A.
Average Inhibition 7 DAT 21 DAT Treatment Rainfall Roundup Roundup 1% L-77 Roundup 1% L-77 1% Glycerin Roundup 1% L-77 2% Glycerin Roundup 1% L-77 5% Glycerin Roundup 1% L-77 10% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" Ju intra. Alternatively, the silicone glycol-silicone alkane terpolymer adjuvant may be added directly to a water solution or dispersion of herbicide.
i ~i I _r ~~~ii WO 89/1'2394
I
PCT/US89/0257) -29- EXAMPLE 4 Response 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 1/4 inch of rain was applied approximately one hour after application of herbicide treatments.
All treatments contained Roundup at 1/2 lb ae/A.
Average Inhibition 7 DAT 21 DAT Treatment Rainfall Roundup Roundup 1% L-77 Roundup 1% L-77 1% Propylene Glycol Roundup 1% L-77 2% Propylene Glycol None 1/4" None 1/4" None 1/4" None 1/4" 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 WO 89/12394 PCT/US89/025,70 EXAMPLE 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 1/4 inch 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 (Ib ae/A) 0.125 0.375 Treatment Rainfall Mean 72 38 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 10% Glycerin Roundup 1% L-77 Roundup 1% L-77 10% Glycerin Roundup 0.25% SF-1188 Roundup 0.25% SF-1188 10% Glycerin Roundup 1% SF-1188 Roundup 1% SF-1188 10% Glycerin Roundup 10% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 72 100 98 78 99 97 96 72 100 96 96 43 100 100 100 weight ratio of herbicide active ingredient to aajuvant 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.
I I ,WO 89/12394 PCT/US89/02570 -31- 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 1/4 inch 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 (lb ae/A) 0.125 0.375 Treatment Rainfall Mean 58 44 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% PEG-200 Roundup 0.25% L-77 10% PEG-200* Roundup 0.50% L-77 Roundup 0.50% L-77 5% PEG-200 Roundup 0.50% L-77 10% PEG-200 Roundup 1% L-77 Roundup 1% L-77 5% PEG-200 Roundup 1% L-77 10% PEG-200
HO(CH
2 CH0O) H n None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkyl phenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the fatty acid esters of hexito anyhydrides WO 89/12394 PCT/US89/0257h -32- 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 rainfall treatment. Simulated rainfall equivalent to 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 2. days after treatment.
Roundup Rate (lb ae/A) 0.25 0.75 Treatment Rainfall None 1/4" Mean 56 12 Roundup Roundup 1% SF-1188* Roundup 1% SF-118P 1.25% Glycerin Roundup 1% SF-1188 2.5% Glycerin Roundup 1% SF-1188 5% Glycerin Roundup 1% SF-1188 10% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 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.
(lij__i_~ I VO 89/ f2394 PCT/US89/02570 -33- EXAMPLE 8 Response of seedling johnsongrass to Roundup and tank mixtures containing Roundup L-7607 and Roundup L-7607 Glycerin with and without simulated ra'nfall treatment. Simulated rainfall equivalent to 1/4 inch 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 (Ib ae/A) 0.125 0.375 Treatment Rainfall Mean 49 Roundup Roundup 1% L-7607 Roundup 1% L-7607 1% Glycerin Roundup 1% L-7607 3% Glycerin Roundup 1% L-7607 5% Glycerin Roundur 1% L-7607 10% Glycerin None 1/4" Non& 1/4" None 1/4" None 1/4" None 1/4" None 1/4"
L
i WO 89/12394 PCT/US89/02570 -34- 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 1/4 inch 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 (Ib ae/A) 0.125 0.375 Treatment Rainfall Mean 49 Roundup Roundup 1% SF-1188 Roundup 1% SF-1188 1% Glycerin Roundup 1% SF-1188 3% Glycerin Roundup 1% SF-1188 5% Glycerin Roundup 1% SF-1188 10% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" WO~ 89/1'2394 PCI- US89/02570 EXAMPLE Response of yellow nutsedge to Roundup and tank mixtures containing Roundup L-77 and Roundup L-77 Glycerin with and without rainfall treatment. Simulated rainfall equivalent to 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. Data show average percent growth inhibition at 28 days after treatment.
Roundup Rate (lb ae/A) Treatment Rainfall 1.0 2.0 3.0 Mean Roundup None 50 77 85 71 1/4" 23 47 73 47 Roundup 0.25% L-77 None 45 67 96 69 1/4" 45 82 57 61 Roundup 0.25% L-77 None 70 88 90 82 2.5% Glycerin 1/4" 52 58 73 61 Roundup 0.25% L-77 None 57 85 99 Glycerin 1/4" 57 67 72 Roundup 0.25% L-77 None 65 74 78 72 10% Glycerin 1/4" 47 s5 65 69 Roundup 1% L-77 None 65 75 87 76 1/4" 60 73 73 69 Roundup 1% L-77 None 67 84 80 77 2.5% Glycerin 1/4" 58 70 79 69 Roundup 1% L-77 None 70 88 90 83 5% Glycerin 1/4" 53 63 90 69 Roundup 1% L-77 None 89 93 99 94 10% Glycerin 1/4" 77 63 92 77 WO 89/12394 PCT/US89/02570 -36- 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 1/4 inch 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 (Ib ae/A) 0.125 0.375 Treatment Rainfall Mean 54 34 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% Sorbitol Roundup 0.25% L-77 10% Sorbitol Roundup 10% Sorbitol* CH0OH
(CHOH)
4 None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" iU spraying preLure UJ CWU,- IV Y.
The chemical compositions illustrative of compositions of this invention used in the tests were N'O 89/1'2394 PCT/US89/0257( -37- 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 1/4 inch 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 (Ib ae/A) 0.125 0.375 Treatment Rainfall None 1/4" Mean 56 48 Roundup Roundup 0.05% L-77 Roundup 0.05% L-77 2.5% Glycerin Rourdup 0.05% L-77 5% Glycerin Roundup 0.05% L-77 10% Glycerin Roundup 0.10% L-77 Roundup .10% L-77 2.5% Glycerin Roundup 0.10% L-77 5% Glycerin Roundup 0.10% L-77 10% Glycerin Roundup 0.30% L-77 Roundup 0.30% L-77 2.5% Glycerin Roundup 0.30% L-77 5% Glycerin Roundup 0.30% L-77 10% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" Jone 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 38 99 100 98 100 99 8 84 100 83 99 99 99 98 18 87 88 99 98 99 99 WO 89/12394 PCT/US89/02570 -38- 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 1/4 inch 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 (lb ae/A) 0.125 0.375 Treatment Rainfall Mean 3 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 10% Glycerin Roundup 1% L-77 Roundup 1% L-77 10% Glycerin Roundup 0.25% L-7607 Roundup 0.25% L-7607 10% Glycerin Roundup 1% L-7607 Roundup 1% L-7607 10% Glycerin Roundup 0.25% SF-1188 Silicone surfactant None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" i I I VO 89/112394 NO89/~2394PCT/IUS89/0257f) -39- Roundup Rate (lb ae/A) 0.125 0.375 Treatment Rainf all Mean Roundup 0.25%/ SF-1188 10% Glycerin Roundup 1% SF-1188 Roundup 10/ SF-1188 10% Glycerin Roundup 10% Glycerin None 1 /4" None 1 /4" None 1/4" None 1/411 100 72 8 4 WO 89/12394 PCT/US89/02570 EXAMPLE 14 Response of downy brome to Roundup and tank mixtures containing Roundup and Roundup L-77 Glycerin with and without simulated rainfall treatment. Simulated rainfall equivalent to 1/4 inch of rain was applied approximately one hour aftapplication of herbicide treatments. Data show averagt percent growth inhibition at 28 days after treatment.
Roundup Rate (Ib ae/A) Treatment Rainfall 0.375 0.75 Mean 63 6 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 None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 100 100 28 73 1 r WO 89/r2394 PCT/US89/02570 -41- EXAMPLE Response of seedling johnsongrass to Roundup and tank mixtures containing Roundup L-77 and Roundup L-77 Humectant with and without simulated rainfall treatment. Simulated rainfall equivalent to 1/4 inch 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 (lb ae/A) 0.125 0.375 Treatment Rainfall Mean 54 18 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% Glycerin Roundup 0.25% L-77 5% Dextrose Roundup 0.25% L-77 5% Sodium Lactate* Roundup 0.25% L-77 5% Lactic Acid* Roundup 0.25% L-77 5% Triethylene Glycol Roundup 0.25% L-77 5% PEG-200 Roundup 0.25% L-77 5% Cane Molasses* Roundup 1% Dextrose None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" Humectants
I
WO 89/12394 Roundup Roundup Roundup Glycol Roundup Roundup -42- Roundup Treatment Rainfall 01 5% Sodium Lactate Norz 75 1/4"1 2 5% Lactic Acid None 40 1/4" 0 5% Triethylene None 67 1/4"1 0 5% PEG-200 None 62 1/4" 2 50% Cane Molasses None 1/4" PC'T/US89/O257.
.ate (lb ae/A) 5 0.375 100 27 82 33 99 10 99 25 Me an 88 14 61 17 83 13 WO 89/12394 PCT/US89/0257( -43- EXAMPLE 16 Response of seedling johnsongrass to Roundup and tank mixtures containing Roundup L-77 and Roundup L-77 humectant at different 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 (lb ae/A) 0.125 0.375 Treatment Mean Roundup Roundup 0.01% L-77 Roundup Roundup Roundup Roundup Roundup Roundup 0.01% 0.01% 0.01% 0.01% 0.01% 0.01% L-77 L-77 L-77 L-77 L-77 L-77 0.25% 0.50% 1.00% 0.25% 0.50% 1.00% Glycerin Glycerin Glycerin
TEG*
TEG
TEG
Roundup 0.025% L-77 Roundup Roundup Roundup Roundup Roundup Roundup 0.025% 0.025% 0.025% 0.025% 0.025% 0.025% L-77 L-77 L-77 L-77 L-77 L-77 0.025% Glycerin 0.50% Glycerin 1.00% Glycerin 0.25% TEG 0.50% TEG 1.00% TEG Roundup 0.05% L-77 Roundup Roundup Roundup 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% L-77 L-77 L-77 L-77 L-77 L-77 0.50% 1.00% 2.50% Glycerin Glycerin Glycerin Roundup Roundup Roundup 0.50% TEG 1.00% TEG 2.50% TEG Triethylene glycol 1/4" U 4U/ LU WO089/12394PC/S802O -44- Roundup Rate (lb ae/A) 0.125 0.375 Treatment Roundup 0.10% L-77 Mean 8 8 72 Roundup Rou nd up Roundup 0.10% 0.10% 0. 10% 0. 10% 0.10% 0. 10% L- 77 L- 77 L-77 L- 77 L- 77 L- 77 0.50% 1.00% 2.50% Glycerin Glycerin Glycerin Roundup Roundup Roundup 0.50% TEG 1.00% TEG 2.50% TEG
HO(CH
2
CH
2 0) H n II I i WO 89/12394 PCrIUS89/O2570 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. Simulated rainfall equivalent to 1/4 inch 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 (Ib ae/A) 0.0625 0.1875 0.3125 Treatment Rainfall Mean 87 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% Glycerin None 1/4" None 1/4" None 1/4"
L
WO 89/12394 PC/US89/02570 -46- 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 Glyphosate Rate (lb ae/A) Average Inhibition Crabgrass Pigweed Roundup 0.0625 0.1875 0.3125 0.4375 Mean 20 96 98 100 76 0 33 72 78 Roundup 0.25% L-77 0.0625 0.1875 0.3125 0.4375 0 100 100 100 100 100 100 94 100 100 100 99 Mean Roundup 0.25% L-77 5% Glycerin 0.0625 0.1875 0.3125 0.4375 91 Mean ,i'i.LCu.r:\ii-I.-.lir:ll; ._~Ill:~Li iili:LL1 b~i, i 1- i WOo 89/f2394 PCT/US89/02570 -47- 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 1/4 inch 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 (Ib ae/A) Weed Treatment Species Rainfall 0.3125 0.4375 Mean Roundup Downy Brome Velvetleaf Roundup 0.25% L-77 Downy Brome Velvetleaf None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" Roundup 0.25% L-77 5% Glycerin Downy Brome Velvetleaf
I
WO 89/12394 WO 8912394PCT/US89/02570 -48- EXAMPLE 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 La.
the absence of simulated rainfall treatment. Data show average growth inhibition at 21 days after treatment.
Roundup Rate (lb ae/A) Treatment 0.125 0.375 Mean Roundup Roundup 0.250 L-77 Roundup 0.25% 1 -77 5% Glycerin MON-0139/M0N-0818*** (2:1) MON-0139/MON-0818 0.25% L-77 M0N-0139/M0N-0818 0.25% L-77 MON-0139/M0N-0818 (4:1) MON-0139/MON-0818 0.25% L-77 MON-0139/MON-0818 0.25% L-77 5% Glycerin 5% Glycerin 5% Glycerin MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/IION-0818 1) 0.25% L-77 0.25% L-77 MON-0139/Arquad* T50 (2:1) MON-0139/Arquad T50 0.25% L-77 MON-0139/Arquad T50 0.25% 1-77 MON-0139/Arquad MON-0139/Arquad MON-0 139/Arquad M0N-0 139/Arquad M0N-0139/Arquad MON-0139/Arquad T50 (4:1) T50 0.25% L-77 T50 0.25% L-77 T50 (8:1) T50 0.25% L-77 T50 0.25% L-77 5% Glycerin 5% Glycerin 5% Glycerin M0N-0139/Ethoquad** 0-25 (2:1) tON-0139/Ethoquad 0-25 0.25% 1-77 M0N-0139/Ethoquad 0-25 0.25% L-77 MON-0139/Ethoquad 0-25 (4:1) MON-0139/Ethoquad 0-25 0.25% L-77 MON-0139/Ethoquad 0-25 0.25%4 1-77 5% Glycerin 5% Glycerin
I
WO 89/12394 '~VO 81f2394PCT/US89/0257() -49- Roundup Rate (lb ae/A) Treatment 0.125 0.375 Iean M1N-0139/Ethoquad 0-25 20 99 59 ti0N-0139/Ethoquad 0-25 0.25% L-77 7 33 MON-0139/Ethoquad 0-25 0.25% L-77 5% Glyce-in 99 100 99 Formula C 18
H
35
-N+-(CH
2
CH
2 0),H
(CH
2
CH
2 0) mH m n total Formula I
R-N-CH
3 Cf- R is from tallow Formula (2CH2 0 mH
(>CH
2
CH
2 0) n H
H(CH
2
CH
2 O) pH m-$n+p R is from tallow WO 89/12394 WO 8912394PCF/ US89/02570 Roundup Rate (lb ae/A) 0.125 0.375 Mean Treatment MON-0139/Arquad ,MON-0139/Arquad MON-a 139/Arquad MON-a 139/Arquad .MON-a 139/Arquad MON-0139/Arquad MON-a 139/Arquad .MON-a 139/Arquad MON-a 139/Arquad B-100* (2:1) B-100 0.25% L-77 B-l00 0.25% L-77 74 100 B-10a B-100 B-10O B-100 B-100 (4:1) 0.25% L-77 0.25% L-77 (8:1) 0.25% L-77 0.25% L-77 5% Glycerin 5% Glycerin 5% Glycerin 77 100 25 73 99 100 33 100 23 73 99 100
CH
2 -0-
I
R-N-CH
3
C~H
3 Cl- R fatty acid O89/1 2394 PCT/U.S89/025-'70 -51- EXAMPLE 21 Response of velvetleaf to glyphosate formulations containing quaternary ammionium 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 (lb ae/A) Treatment 0.3125 0.50 Mean Roundup Roundup 0.25*4 L-77 Roundup 0.25% L-77 5% Glycerin MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/MON-0818 MON-0139/MON-0818 MON -0139 /MON- 0818 MON-0139/MON-0818 (2:1) 0.25% L-77 0.25% L-77 (4:1) 0.25% L-77 0.25% L-77 (8:1) 0.25% L-77 0.25% L-77 5% Glycerin 5% Glycerin 5% Glycerin MON-0139/Arquad T50 (2:1) MON-0139/Arquad T50 0.25% L-77 MON-0139/Arquad T50 0.25% L-77 5% Glycerin MON-a 139/Arquad MON-a 139/Arquad MON-a 139/Arquad MON-a 139/Arquad MON-0139/Arquad MON-a 139/Arquad MON-a 139/Ethoquw MON-a 139/Ethoqu, MON-a 139/Ethoqu MON-O139/Ethoqu MON-0139/Ethoqu MON-a 139/Ethoqu, 750 (4:1) T50 0.25% L-77 T50 0.25% L-77 T50 (8:1) T50 0.25% L-77 750 0.25% L-77 0-25 0-25 0-25 0-25 0-25 0-25 (2:1) 0. 25% L 0 .250% L' (4:1) 0 .250;1 L 0. 25'1, L 5% Glycerin 5% Glycerin -77 -77 5% Glycerin -77 -77 5%4 Glycerin WO 89/123~ PCV/LS89/O25~() WO 89/123, PCF/US89/02-570 -52- Roundi Treatment MON-0139/Ethoquad 0-25 (8:1) M0N-0139/Ethoquad 0-25 0.25% L-77 MON-0139/Ethaoquad 0-25 0.25% L-77 5% Glycerin up Rate (lb ae/A) 0.3125 0.50 Mean 7 47 r3 75 86 MON-0139/Arquad MON-0139/Arquad 11N-0139/Arquad MON-0139/Arquad tlN-0139/Arquad MON-0139/Arquad M0N-0139/Arquad MIN-0139/Arquad MON-0 139/Arquad B-100 B-100 B-100 B-100 B-100 B-100 B-100 B-100 B-100 1) 0.250% L-77 0.25% L-77 5% Glycerin 0.25% L-77 0.25% L-77 1) 0.25% L-77 0.25% L-77 5% Glycerin 5% Glycerin _Y1Yiii;;_ i i WO~ 89/12394 DCI7 US89/02570 -53- EXAMPLE 22 The effect of different surfactant types on the efficacy and rainfastness of glyphosate L-77 glycerin tank mixtures on seedling jonnsongrass and barnyardgrass. Simulated rainfall equivalent to 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 3/8 lb ae/A. Data show average percent growth inhibition at 27 days after treatment.
Treatment Seedling johnson- Rainfall grass Average Barnyardgrass Inhibition 73 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% Glycerin MON-0139 0.09% MON-0818 MON-0139 0.09% MON-0818 0.25% L-77 MON-0139 0.09% MON-0818 0.25% L-77+ 5% Glycerin MON-0139 0.09% Witconate X-7163* MON-0139 0.09% Witconate X-7163 0.25% L-77 MON-0139 0.09% Witconate X-7163 0.25% L-77 5% Glycerin MON-0139 0.09% Ethoquad** C/12 MON-0139 0.09% Ethoquad C/12 0.25% L-77 None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" WO 89/12394 WO 8912394PCT/ US89/0257O -54wherein Witconate X-7163 is of the formula nCH 2 1 0S0 3
~CH
3
CH
3 wherein n 8 to Treatment Seedling Johnson- Barnyard- Rainfall grass grass Average 0% Inhibition MON-0139 0.09% LE'hoquad C/12 0.25%4 L-77 50% Glycerin MON-0139 0.09%4 Sorpol 8227 MON-0139 0.09% Sorpol 8227 0.25% L-77 MON-0139 0.09% Sorpol 8227 0.250% L-77 5% Glycerin MON-0139 0.09% Ethomeen C/12 MON-0139 0.0904 Ethomeen C/12 0.25% L-77 MON-0139 0.09% Ethomeen C/12 0.25% L-77 5% Glycerin MON-0139 0.09% Igepa~l CA-720 MON 0139 0.09% Igepal CA-720 0.25% L-77 MON-0139 0.09% Igepal CA-720 0.25% 1-77 5% Glycerin MON-0139 0.09% Nonylphenol blend MON-0139 0.09% Nonylphenol blend 0.25% L-77 None 1/4? None 1/4?? None 1/4"1 None 1/411 None 1 None 1/4? None 1 /4"1 None 1/4"1 None 1 /4" None 1 /4" None 1/4"1 None 1/4" 100 100 100 17 4.2 8 9:3 91 98 27 38 13 100 97 98 68 12 13 100 97 100 3 18 Roundup 5% Dextrose None 1/411 Humectants WO089/12394 PCT/US89/025"() Treatment Seedling johnson- Barnyard- Rainfall grass grass Average O/4 Inhibition MON-0139 0.09% Nonyiphenol blend 0.25% L-77 5% Glycerin MON-0139 0.09% Sterox NJ MON-0139 0.09% Sterox NJ 0.25% L-77 None 1/4" None 1 /4" None 1 /4" Igepal CA-720 Sterox NJ
C
8
H
1 7 HH2
C
H0) 12*5 CqH 9 0 -H2
C
H2) 9 5
H
CH
2
CH
2 0H Sorpol 8227 mix of C 1 2
H
2 5 N-4CH 3
CH
2
CH
2 0H with alkyl phenol ethoxylate
CH
2
CH
2 0H 1+
R-N--CH
3 Ethoquad C/12 is Cl1 whe re
CH
2
CH
2 0H R is from coco fatty acid.
Ethomeen C/12 is
CHCH
2
OH
'-CH
2
CH
2 0H where R is from coco fatty acid.
WO 89/12394 WO 8912394PCT/ US89/025-70 -56- Treatment Seedling j hn son Rainfall grass Average Barnya rdgrass SInhibition MON-0139 0.09% Sterox NJ 0.25% L-77 5% Glycerin MON-0139 0.09% Miranol CM-SEX tON-0139 0.09% Miranol CM-SEX 0.25% L-77 MON-0139 0.09% Miranol CM-SFK 0.25% L-77 5% Glycerin MON-0139 0.09% Aerosol MA-8O MON-0139 0.09% Aerosol MA-8O 0.25% L-77 MON-0139 0.09% Aerosol MA-80 0.25% L-77 5% Glycerin MON-0139 0.09% Frigate MON-0139 0.09% Frigate 0.25% L-77 MON-0139 0.09% Frigate 0.25%4 L-77 5% Glycerin None 1 /4" None 1 /4" None 1 /4"1 None 1/4" None 1/4" None 1 /4" None 1/4"1 None 1 /4" None 1 /4"1 None 1/411 Aerosol HA-80 is 0 0 I1 1 1
C
6
H
1 3 0-C-CH-CH 2 -C-0-C 6
H
13 S03-Na+ Frigate is a based adjuvant tallow amine ethoxylate.
I
I
iU Roundup 0.05% L'-77 Roundup 0.05% L-77 Roundup 0.05% L-77 0.50% TEG 1.00% TEG 2.50% TEG Triethylene glycol W O 89/1'2394 PCTF/U1S89/0257() -57- Miranol CM-SFK
R-CI
where
CH
2 COO-Na+
C
2
H
4
OH
R is a coco Fatty acid or 0 CH 2
CH
2
OH
1 1
R-CNHCH
2
-CH
2
-N-CH
2 COO -Na+ WO 89/12394 PCT/US89/02570 S' I -58- 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 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 3/8 Ib ae/A. Data show average percent growth inhibition at 27 days after treatment.
Treatment Seedling johnson- Rainfall grass Average Barnyardgrass Inhibition 88 Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 5% Glycerin Sodium Glyphosate 0.09% MON-0818 Sodium Glyphosate 0.09% MON-0818 0.25% L-77 Sodium Glyphosate 0.09% MON-0818 0.25% L-77+ 5% Glycerin Potassium Glyphosate 0.09% MON-0818 Potassium Glyphosate 0.09% MON-0818 0.25% L-77 Potassium Glyphosate 0.09% MON-0818 0.25% L-77 5% Glycerin Copper Glyphosate 0.09% MON-0818 Copper Glyphosate 0.09% MON-0818 0.25% L-77 None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" II WO 89/ f2394 PCT! LS89/02570I -59- Seedling j ohns on Barnyard- Treatment Rainfall grass grass Average %Inhibition Copper Glyphosate 0.09% MON-0818 None 100 72 0.25% L-77 5% Glycerin 1/4" 96 67 IPA Glyphosate 0.09% MON-0818 None 100 78 1/411 35 48 IPA Glyphosate 0.09% MON-0818 None 58 38 0.25% L-77 1/4"1 15 22 IPA Glyphosate 0.09% MON-0818 None 100 88 0.25% L-77 5% Glycerin 1/4" 88 Ammionium Glyphosate 0.09% MON-0818 None 100 89 1/4" 32 38 Ammonium Glyphosate 0.09% MON-0818 None 88 81 0.25% L-77 1/4"1 7 23 Amnmonium Glyphosate 0.09% MON-0818 None 100 88 0.25% L-77 5% Glycerin 1/4" 86 82 WO 89/12394 PCT/ULS89/02570 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 1/4 inch of rain was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 3/8 lb ae/A.
Data show average percent growth inhibition at 26 days after treatment.
Treatment Seedling johnson- Rainfall grass Average Barnyardgrass Inhibition Roundup MON-0139 0.09% MON-0818 MON-0139 0.09% MON-0818 0.25% L-77 MON-0139 0.09% MON-0818 0.25% L-77 5% Glycerin MON-0139 0.09% MON-0818 0.25% L-77 5% Dipropylene glycol MON-0139 0.09% MON-0818 0.25% L-77 5% Ethylene glycol MON-0139 0.09% MON-0818 0.25% L-77 5% Butanol MON-0139 0.09% MON-0818 0.25% L-77 5% Glucose MON-0139 0.09% MON-0818 0.25% L-77 5% Fructose MON-0139 0.09% MON-0818 0.25% L-77 5% Sucrose None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 100 37 97 7 100 100 69 27 57 96 32 99 93 100 96 100 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 cs a surfactant.
~1 WO 89/12394
J
PCT/ US89/0257 -61- EXAMPLE Response of seedling johnsongrass, barnyardgrass and velvetleaf to tank mixtures containing ammonium glyphosate and L-77 with low level of glycerin for efficacy and rainfastness. Simulated rainfall equivalent to 1/4 inch of rainfall was applied approximately one hour after application of herbicide treatments. All treatments contained glyphosate at 3/8 lb ae/A. Data show average percent growth inhibition at 28 days after treatment.
Treatment Seedling johnson- Rainfall grass Avera Barnyard- Velvetgrass leaf ge Inhibition Roundup Roundup 0.25% L-77 Roundup 0.25% L-77 1% Glyceriu Roundup 0.25% L-77 Glycerin Ammonium Glyphosate 0.09% MON-0818 Ammonium Glyphosate 0.09% MON-0818 0.25% L-77 Ammonium Glyphosate 0.09% MON-0818 0.25% L-77 1% Glycerin Ammonium Glyphosate 0.09% MON-0818 0.25% L-77 5% Glycerin None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" None 1/4" 47 100 100 98 22 13 87 33 100 100 M0N-0139/Ethoquad 0-25 0.25% L-77 MON-0139/Ethoquad 0-25 (4:1) M0N-0139/Ethoquad 0-25 0.25% L-77 MON-0139/Etiioquad 0-25 0.25% L-77 5% Glycerin 6 0 62 100 48 98 73 18 33 26 5% Glycerin 95 100 98 WO 89/12394 PC[/US89/025q() -62- Treatment Seedling johnson- Barnyard- Velvet- Rainfall grass grass leaf Average Inhibition Anwoniun Glyphosate 0.09% Ethoqulad C/12 Amnmoniumn Glyphosate 0.09% Ethioquad C/12 0.25% L-77 Amnmoniumn Glyphosate 0.09% Ethoquad C/12 0.25% L-77 1% Glycerin Amnmoniumn Glyphosate 0.09% Ethoquad C/12 0.25% L-77 5% Glycerin None 1 /4" None 1 /4"1 None 1/41" None 1/4" 72 0 100 88 100 100 100 WO 89/12394 PCT/US89/02570 -63- EXAMPLE 26 Response of certain broadl af 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.
Treatment Blazer herbicide Blazer 0.5% Triton AG-98 Blazer 0.5% Triton AG-98 0.5% L-77 Blazer 0.5% Triton AG-98 0.5% L-77 Glycerin Herbicide Rate (Ib ai/A) 0.125 0.375 Cockle- Morning- Velvet- Hemp bur 0 3 glory 0 0 leaf 0 0 Sesbania 33 Blazer 0.5% L-77 Blazer 0.5% L-77 10% Glycerin Blazer 0.5% X-45 10% Glycerin Blazer 0.5% X-45* 0.5% L-77 10% Glycerin Blazer 0.5% Triton AG-98 0.5% Igepal CA-210 10% Glycerin Blazer 0.5% L-77 0.5% Igepal CA-630 10% Glycerin 0.125 0.375 0.125 0.375 0.125 0.317 0.125 0.375 0.125 0.375 0.125 0.375 0.125 0.375 0.125 0.375 0.125 0.375 47 97 47 100 72 97 28 100 27 77 57 100 48 97 32 53 37 100 X-45, Blazer humectant only WO 89/12394 Triton AG-98 Triton X-45 Igepal CA-630 Igepal CA-210 PCTF/1S89/02570 -64- Tank mix adjuvant, alkylaryl polyoxyethylene glycols
CSH-
17 0-(CH 2
CH
2
O)SH
C
8
H
7 -0-(CH 2
CH
2 9
H
C
8
H
1 7 -0 -(CH 2
CH
2 O)1. SH r*ri I-- IWO 89/12394 PCT/US89/02570 EXAMPLE 27 Response of seedling johnsongrass and barnyardgrass to postemergence treatments of herbicide tank mixtures containing imazaquin (Scepters herbicide) L-77 Glycerin. Scepter was applied at 0.375 lb ai per acre. Data show average percent growth inhibition at 21 days after treatment. means active ingredient.) Treatment Scepter herbicide Scepter L-77 Scepter L-77 Glycerin Seedling johnsongrass 27 47 57 Barnyardgrass 27 53 Scepter Triton X-45 Glycerin 63 ;I c 111 1.1 IIjI I AXM,,,rUS85dONW'" I ,W*t I 06,'~,~zX-nsbowj jfp)i'P" zAxmAfl1saJdONW1)IflN')i3( )OV I~d el 068L9Pt' zAxMAnsbdoUWj!~OP~qO ZAXMAn1SOdoNWN~rHJa)V 'Id 0L II 11111JI W .25 11114BL I I III I I I I WO 89/12394 PCT/ LS89/0257( -66- EXAMPLE 28 Response of barnyardgrass to tank mixtures containing Roundup@, Silicone Fluid and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Roundup@ was applied at 3/8 lb ae/A, Fluid at 0.25% and glycerin at 2.5% The spray galloaage was equivalent to 20 gallons per acre of spray solution.
Average Inhibition (25 DAT) 0 Rain 1/4" Rain Glycerin Glycerin Glycerin Glycerin Treatment Roundup Roundup Fluid 3 Roundup Fli'id 7 Roundup Fluid 8 Roundup Fluid 4 Roundup Fluid 6 Roundup Fluid where fluids are defined hereinafter and are useful as Silicone surfactants herein.
means without means with WO 89/12394 PC'F/US89/025-/' -67- EXAMPLE 29 Response of barnyardgrass to tank mixtures containing Roundup@, Fluid and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 27 days after treatment. Roundup@ was applied at 3/8 lb ae/A, Fluid at 0.25% and glycerin at 5% The spray gallonage was equivalent to 20 gallons per acre of spray solution.
Average Inhibition (25 DAT) 0 Rain Rain Glycerin Glycerin Glycerin Glycerin Treatment: Roundup Roundup Fluid 1 Roundup Fluid 5 100 100 5 100 WO 89/12394 PCT/ S89/025'70 1 -68- EXAMPLE Response of-barnyardgrass to tank mixtures containing Roundup®, Fluid and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 23 days after treatment. Roundup@ was applied at 3/8 lb ae/A, Fluid at 0.5% and glycerin at 5% The spray gallonage was equivalent to 20 gallons per acre of spray solution.
Treatment Average Inhibition (25 DAT) 0 Rain 1/4" Rain Roundup Roundup Glycerin Roundup Fluid 9 Roundup Fluid 9 Glycerin i SWO 89/12394 PCT/US89/02570 -69- EXAMPLE 31 Response of barnyardgrass to tank mixtures containing Roundup@, Fluid and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 24 days after treatment. Roundup@ was applied at 1/2 lb ae/A, Fluid at 1% The spray gallonage was equivalent to gallons per acre of spray solution.
Treatment Average Inhibition (25 DAT) 0 Rain 1/4" Rain Roundup Roundup Fluid 6 Roundup Fluid 6 1% Glycerin Roundup Fluid 6 3% Glycerin Roundup Fluid 6 5% Glycerin 100 WO 89129 PC-TI US89/0257 WO 89/12394 PC'F/US89/0257/0 EXAMPLE 32 Response of barnyardgrass to tank mixtures containing Roundup@, Fluid and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 26 days after treatment. Roundup@ was applied at 3/8 Ib ae/A, Fluid at 0.25% The spray gallonage was equivalent to 20 gallons per acre of spray solution.
Treatment Average Inhibition (25 DAT) 0 Rain 1/4" Rain Roundup Roundup Fluid 2 Roundup Fluid 2 1% Glycerin Roundup Fluid 2 2.5% Glycerin Roundup Fluid 2 5% Glycerin Roundup 5% Glycerin I 1.
SWO 89/1,2394 PCT/US89/02570 -71- EXAMPLE 33 Response of rhizome johnsongrass to tank mixtures containing Roundup@, Fluid and glycerin in the ibsence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 23 days after treatment. Roundup@ was applied at 3/8 Ib ae/A and glycerin at 1% The spray gallonage was equivalent to 20 gallons per acre of spray solution.
Treatment Average Inhibition (25 DAT) 0 Rain 1/4" Rain Roundup Roundup 0.125% Fluid 6 Glycerin Roundup 0.25% Fluid 6 Glycerin Roundup 1% Fluid 6 Glycerin Roundup 1% Fluid 6 99 WO 89/12394 PCT/ US89/02570 -72- EXAMPLE 34 Response of rhizome johnsongrass to tank mixtures containing Roundup®, Fluids and glycerin in the absence or presence of 1/4 inch simulated rainfall applied one hour after treatment. Data show average percent growth inhibition 22 days after treatment. Roundup@ was applied at 1/2 lb ae/A and Fluids 0.5% The spray gallonage was equivalent to 20 gallons per acre of spray solution.
Average Inhibition (25 DAT) Silicone Additive
NONE
Fluid 11 Glycerin Con.
0 Rain 1/4" Rain Fluid 7 Fluid 8 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 Fluid 6 Fluid 10 Note: Glycerin concentration is expressed as of the total spray volume based on a spray gallonage equivalent to 20 galons/A.
Fluid 11 is a material of Formula IV wherein Q and R are both methyl, x and y are both zero, G is -CH 2
CH
2
CH
2
(CH
2
CH)
7 OC=OMe and z is 1.
c I I WO 89/1,2394 W089/'2394PCF/L S89/02570 -73-
FLUIDS
Me3SiO(SiMe 2 O)X( SiMeAO)y(SiMeGO)zSiMe3 FLUID ALKANE
CHAIN
LENGTH
UNITS
EO
UNITS
GLYCOL DIIIETHYL UNITS UNITS Wx 0.90 1.32 0.50 1.50 0.64 0.64 0.50 0.25 2.00 1.00 4.60 2.68 5.00 2.50 1.36 1.36 3.50 1.75 9.00 4.50 0.0 0.0 0.0 19.0 all wherein G is -CH 2
CH
2
CH
2
(OCH
2
CH
2 )m OC=OMe
I
Claims (40)
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Claims (40)
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1. An enhanced herbicidal composition comprising a herbicidally effective amount of a herbicide, humectant, and silicone surfactant.
2. The herbicide composition of Claim 1 wherein said herbicide is selected from the group consisting of acifluorfen (5-(2-chloro-aaa-trifluoro- p-tolyloxy)-2-nitrobenzoic acid and its agriculturally SI. acceptable salts thereof; oxyfluorfen (2-chloro-l- 10 (3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene; lactofen, (1'-(Carboethoxy)ethyl
5-'2-chloro-4-(tri- fluoromethyl)phenoxyl -2-nitrobenzoate; imazaquin (2-'4,5-Dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH- S" imidazol-2-- yl'-3-quinolinecarboxylic acid and the 15 agriculturally acceptable salts thereof, N-phosphono- methylglycine and/or an agriculturally acceptable salt thereof, mixtures thereof and the like. 3. The herbicide composition of Claim 2, wherein said herbicide is N-phosphonomethylglycine 20 or an agriculturally acceptable salt thereof. 4. The herbicide composition of Claim 3, wherein said agriculturally acceptable salt of N-phosphonomethylglycine is the isopropylamine salt. The herbicide composition of Claim 3, which comprises the isopropylamine salt of N-phosphono- methylglycine, Silwet L-77, and humectant. i
09-21(2873)A 6. The herbicidal composition of Claim 1 wherein said silicone surfactant comprises a poly- alkylene oxide modified dimethylpolysiloxanes rnn^~IrmartI having the average general formula: CH:, CH CH 3 CHa H 3 Si- Si----Si-C (I) L-I I( CH 3 CHa C3aH CHa x Y (C2H 4 0)a(C 3 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 can be hydrogen or a lower alkyl radical having 1-3 carbon atoms or an acyl group having 2 to 4 carbon atoms. 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 of claim 1, wherein said silicone surfactant is a compound of the 25 Formula R R QR 2 SiO(SiR 2 0)x(SiO) (SiO)zSiR 2 Q i I 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 Sc. is a glycol moiety having the formula -R'(OCH 2 CH 2 )mOZ, WO 89/1'2394 PCT/US89/02570 -76- 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 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 9. The herbicidal composition of claim 8, wherein said silicone surfactant is a compound of the average Formula Me Me I I Me3SiO(SiO)o. 64 (SiO) 1 36 SiMe 3 -CH 2 CH 2 CH 2 (OCH2 2 24 0C(0)CH 3 -(CH2) 11 CH 3 wherein Me denotes a methyl radical. The composition of claim 1, wherein said herbicide is N-phosphonomethylglycine or an agriculurally acceptable salt thereof and said silicone surfactant is selected from the group consisting of those having the average formula Me Me 3 SiO(SiO)SiMe 3 (III) C 3 H 6 -O(C 2 H40)a(C 3 H 6 O)bZ 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 -77- 09-21(2873)A having the average formula R R I I Q(R 2 )SiO(SiR 2 0)x(SiO) (SiO) SiR 2 Q (IV) z 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 0 is a glycol moiety having the formula -R'(OCH 2 CH) 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 S 15 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 alkyl radical R; x is 0 to 100, y is 0.1 to 25 and z is 0.1 to
11. The herbicidal composition of claim 20 wherein said silicone surfactant comprises those having the average formula Me Me 3 SiO(SiO)SiMe 3 (III) 25 C3H6-O(C2H40)a(C3H60)bZ 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.
12. The herbicidal composition of claim 10 or 11, wherein said agriculturally acceptable salt of ~lcyc~-~19~1r i -78- 09-21(2873)A N-phosphonomethylglycine is an amine, trimethylsulfonium, or an iminourea salt.
13. The herbicidal composition of any one of Claims 10 to 12, wherein said agriculturally acceptable salt of N-phosphonomethylglycine is the isopropylamine salt.
14. The herbicidal composition of any one of S Claims 1 to 13, wherein said humectant is selected from the group consisting of r- bitol, glycerol. polyethylene glycol, polypropylene glycol, propylene glycol, triethylene glycol, 5 glycerine, sodium stearate, microcrystalline cellulose, homolinear polymers of ethylene oxide, soluble collagen, lactic acid and salts thereof, cane molasses and the like. a a The herbicidal composition of any one of Claims 1 to 14, wherein the concentration of active I ingredient is in the range from about 2 to about 70% by !;eight. iC .l.m 16. The herbicidal composition of any one of Claims 1 to 14, wherein the concentration of said active I ingredient is in the range from about 4 to about 40% by weight.
17. The h-rbicidal composition of any one of Claims 1 to 14, 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.
18. The herbicidal composition of any one of Claims 1 to 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. VO 89/t2394 PCT/LUS89/02570 -79-
19. The composition of Claim 14, wherein the ratio of active ingredient to silicone surfactant is about 1:1. The composition of Claim 16, wherein the ratio of active ingredient to silicone surfactant is in that range from about 1:30 to about 50:1.
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.
22. The composition of Claim 16, wherein the ratio of silicone surfactant to hiunectant is about the same.
23. The composition of Claim 19, wherein the weight ratio of silicone surfactant to humectant 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 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 ii in the range from about 1:2 to about 4:1.
27. A composition of Claim 1, which further comprises inert adjuvants and water. i WO 89/12394 Pcri LS89/02510
28. The composition of Claim 1, wherein said composition is a dry composition.
29. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 1. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 2
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 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 plant with an effective amount of the composition of Claim
34. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 6 WO 89/12394 PCT/ LS89/02,7 -81- 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
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
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
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
39. A herbicidal method of use for killing or controlling weeds which comprises contacting a plant with an effective amount of the composition of Claim 11 A herbicidal method of use for killing or controlling weeds which comprises contacting a 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 Claim 13 e 11 IO MELd OML E -I WO 89/12394 PCT/US89/0250 -82-
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
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
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 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 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 plant with an effective amount of Ile 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 Claim i I I I i -83- 09-21(2873)A
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
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
51. A herbicidal method of use for killing 10 or controlling weeds which comprises contacting a plant with an effective amount of the composition of S: Claim 23 a a
52. A herbicidal method of use for killing S1 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 20 Claim a DATED this 29th day of November, 1990 MONSANTO COMPANY, By its Patent Attorneys, E. F. WELLINGTON CO., By: BRUCE S. WELLINGTON INTERNATIONAL SEARCH REPORT International Application No PCT/US 89/02572 I. CLASSIFICATION OF SUBJECT MATTER (it several classification symools aDoly, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC 4 IPC A 01 N 25/30, A 01 N 57/20 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbols 4 IPC IPC A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT* Category Cilation of Document, with Indication, where appropriate, of the relevant passages 2 Relevant to Claim No. Y FR, A, 2589328 (STAUFFER CHEMICAL CO.) 1-53 7 May 1987 see page 1, lines 25-29; page 3, lines 13-29; page 3, line. 37 page 4, line 2; claims AU, A, 64552/86 (cited in the application Y DE, A, 1950380 (DOW CORNING CORP.) 1-53 23 April 1970 see claims 1,8,9 GB, A, 1225249 (cited in the application) SSpecial categories of cited documents: to later document published after the international filing date document defining the general state of the art which Is or priority date and not in conflict wth the aPolicaton but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international document of particular relevance: the claimed invention fiing date cannot be considered novel or cannot be considered to document which may throw doubts on priority clalm(s) or involve an inventive step which o cited to e lrabish the publication date of another document of particular relevance; the claimed invention citation or other spetial reason (as specified) cannot be considered to Involve an Inventive Steo when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such comoination being obvious to a person Skill d document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search rlatc of Mailing of this International Search Report 4th October 1989 2 6. 10. 89 International Searching Authority Signature of Author EUROPEAN PATENT OFFICE T.K. WILLIS- Form PCTIISA/210 rsecond sheet) (January 198) I V- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8902570 SA 29746 This annex lists the patent familvy membcrs relating to the patent documents cited in the above-mentioned international search report. Th e members are as contained in the European Patent Office EDP file on 24/f10/89 The European [latent Office is in no "iay liable for these particulars i~hich are merely given for the purpose of information. Patent document Publjication Patent famify Publication cited in search report date member(s)' date FR-A- 2589328 07-05 -87 DE-A- 1950380 23-04-70 AU -B- AU-A- DE-A- JP-A- AT-A- BE-A- CH-A- FR-A- GB-A- N L-A- 586293 6455286 363 699 4 62120304 3U0451 740113 533945 2020409 1255249 6915346 06-07-89 07-05-87 07-05-87 0 1-0 6-87 15-06-72 10-04-70 28-02-7 3 10 -0 7-7 0 0 1-12-7 1 14-04-70 For more detaifs about this annex :see Officiaf Journal of the European Patent Office, No. 12/82