USOO85865.04B2

(12) United States Patent (10) Patent No.: US 8,586,504 B2 Wright et al. (45) Date of Patent: Nov. 19, 2013

(54) HERBICIDAL COMPOSITIONS CONTAINING FOREIGN PATENT DOCUMENTS GLYPHOSATE AND A PYRONE ANALOG AU 100.73/92 B 10, 1992 CA 2340240 A1 2, 2000 (75) Inventors: Daniel R. Wright, St. Louis, MO (US); EP O 808 569 A1 11, 1997 Joseph J. Sandbrink, Chesterfield, MO GB 2267 825 A 12/1993 (US); Paul G. Ratliff, Olivette, MO WO 99/00013 1, 1999 WO OO,30452 6, 2000 (US) WO OO,642.57 11, 2000 WO OO/67571 11, 2000 (73) Assignee: Monsanto Technology LLC, St. Louis, WO O1/35740 A2 5, 2001 MO (US) WO 02/21924 A2 3, 2002 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 Exhibit PMH-17 Supplemental Labeling regarding Roundup Pro U.S.C. 154(b) by 0 days. Herbicide by Monsanto, EPA Reg. No. 524-475 (Nov. 1995), 11 pageS. (21) Appl. No.: 13/404,861 Exhibit PMH-18 Notice of Pesticide Registration issued on Oct. 5, 2000, 35 pages. Exhibit PMH-19 EPA Application for Pesticide, ID No. 200405 (22) Filed: Feb. 24, 2012 (Sep. 1995), 33 pages. Exhibit PMH-20-Documentation regarding Starmas Racun/ (65) Prior Publication Data Rumpai Herbicide (bears the year 2003), 10 pages. Exhibit PMH-21—Documentation regarding Starmix Racun/ US 2012/O157309 A1 Jun. 21, 2012 Rumpai Herbicide (Date Unknown), 3 pages. Exhibit PMH-22—article entitled Control of Eucalyptus grandis cut stumps by Keith Little et al., ICFR Bulletin Series, No. 02/98 (1998), 19 pages. Related U.S. Application Data Exhibit PMH-23—article entitled the killing of Eucalyptus grandis (63) Continuation of application No. 10/829.572, filed on multiple-stem cut-stumps in the Karkloof Project by Keith Little et al., ICFR Bulletin Series, No. Mar. 2000, 8 pages. Apr. 22, 2004, now abandoned. Exhibit PMH-24—Site Management and Productivity in Tropical (60) Provisional application No. 60/496,031, filed on Apr. Plantation Forests: A Progress Report (bears the date of Dec. 1999), 22, 2003, provisional application No. 60/552,065, 15 pages. Exhibit PMH-25—article entitled Evaluation of herbicides for con filed on Mar. 10, 2004. trol of Summer-growing weeds on fallows in South-eastern Australia, Australian Journal of Experimental Agriculture, vol. 30, (1990) 15 (51) Int. Cl. pageS. AOIN 57/00 (2006.01) Exhibit PMH-26—article entitled Interaction between glyphosate AOIN 25/00 (2006.01) and fluroxypyr improve mallow control, Crop Protection, vol. 21 (52) U.S. Cl. (2002) by R. Chorbadjian, 5 pages. Exhibit PMH-27 WO 2004/093546 (AU 2004232335 B2), Nov. 4, USPC ...... 504/116.1; 504/128 2004. Applicant Monsanto Technology LLC, 108 pages. (58) Field of Classification Search Exhibit PMH-28 GB 2267 825, Applicant DowElanco, date of USPC ...... 504/116.1, 128 publication Dec. 22, 1993, 29 pages. See application file for complete search history. Exhibit PMH-29 US 5703015 issued Dec. 30, 1997 (inventors Paul D. Berger et al.), 15 pages. (56) References Cited (Continued) U.S. PATENT DOCUMENTS Primary Examiner — Janet Epps-Smith 3,799,758 A 3, 1974 Franz Assistant Examiner — Courtney Brown 4.405,531 A 9, 1983 Franz (74) Attorney, Agent, or Firm — Senniger Powers LLP: 4,692, 184 A 9, 1987 Lee Joseph A. Schaper 5,436,223. A 7/1995 Mulqueen et al. 5,565,409 A 10, 1996 Sato et al. 5,703,015 A 12/1997 Berger et al. (57) ABSTRACT 5,834,006 A 11/1998 Smith et al. 5,883,048 A 3, 1999 Morre et al. The present invention is directed to herbicidal compositions 5.998.332 A 12/1999 Sato et al. or formulations, and to methods of using such compositions 6,063,733. A 5/2000 Berger et al. or formulations to kill, or control the growth and proliferation 6,228,807 B1 5/2001 Kuchikata et al. of unwanted plants. In particular, the present invention is 6,245,713 B1 6, 2001 Brinker et al. directed to herbicidal compositions or formulations, as well 6,277,788 B1 8/2001 Wright 6,455,473 B2 9/2002 Wright as their methods of use, which comprise N-phosphonometh 6,569,809 B1 5, 2003 Sato et al. ylglycine or a herbicidal derivative thereof, a pyridine analog 6,579,831 B1 6, 2003 Harwell or a herbicidal derivative thereof, and optionally one or more 6,677.276 B1* 1/2004 Hacker et al...... 504,127 Suitable Surfactants, with N-phosphonomethylglycine being 6,713,433 B2 3, 2004 Jimoh in excess relative to the pyridine analog. Such compositions 6,723,681 B2 4/2004 Hacker et al. 2002/O123430 A1 9, 2002 Xu et al. cause early visual symptoms of treatment and/or enhanced 2002/0155953 A1* 10/2002 Brigance ...... 504,206 effectiveness or control when applied to the foliage of plants. 2003/OOO4063 A1* 1/2003 Jimoh ...... 504,130 2004/OO77499 A1 4/2004 Graham et al. 26 Claims, No Drawings US 8,586,504 B2 Page 2

(56) References Cited McCormack, M.L. et al., Glyphosate and Triclopyr Mixtures to Con trol Forest Brush, Northeastern Weed Science Society (1981) vol. 35. OTHER PUBLICATIONS p. 218. Exhibit PMH-30 article by R.K. Howell et al. entitled Low Volume McCormack M.L. et al., Timing Triclopyr and Glyphosate Treat Foliar Applications of Triclopyr, Picloram, Imzazpyr and Glyphosate ments on Forest Brush, Northeastern Weed Sci. Soc. (1982) New Mixtures for Rights-of-Way Cleanup, 1998 Proceedings, Southern York, NY. vol. 36, pp. 209-214. McDonald, Philip M. et al., Response of Young Ponderosa Pines, Weed Science Society (1998) 4 pages. Shrubs, and Grasses to Two Release Treatments, USDA Forest Ser Exhibit PMH-31-article by Galen M. Wright et al. entitled vice Res. Note PSW-RN-419-Web 1996, 8 pages. Understory Vegetation Control to Establish Oak Regeneration, North Obenshain, Karen R. et al., Spatial Analysis of Herbicide Decay Central Weed Control Conference Proceedings, Columbus, Ohio, Rates in Louisiana, Environmental Monitoring and Assessment vol. 38 (1983) 2 pages. (1997) vol. 48, pp. 307-316. Exhibit PMH-32—article by M.L. McCormacket al. entitled Timing Seifert John R. et al., Pre and Post Herbicide Applications on Hard Triclopyr and Glyphosate Treatments on Forest Brush, Northeastern wood Seedlings, Proc. North Central Weed Sci. Soc., vol. 47 (1992), Weed Sci. Soc., New York, NY. vol. 36 (1982) 7 pages. p.98. Exhibit SG-1—Letter dated Oct. 20, 2011 from Monash University Sparacino, A.C. et al., Le Controle Des Rubus spp. Presentes Sur Les to IP Organisers Pty Ltd, 2 pages. Rives Des Canaux D'Irrigation et Des Rizieres, 45th International Abdelghani, A.A., Assessment of the Exposure of Workers Applying Symposium on Crop Protection, Gent, May 4, 1993, Part III, Herbicide Mixtures (2,4-D--Roundup, Garlon-3A+Roundup), Tox MFLRA358(a), p. 1018-1025. icity and Fate of These Mixtures in the Environment—Summary Supplemental Labeling for Roundup PRO Herbicide by Monsanto, Report (1995), 70 pages. (1996) EPA Reg. No. 524-475,2 pages. Abdelghani, A.A. et al., Toxicity Evaluation of Single and Chemical Wait, Jim D. etal. Weed Control in Glyphosate Resistant Corn, Dept. Mixtures of Roundup, Garlon-3A, 2,4-D, and Syndets Surfactant to of Agronomy, University of Missouri-Columbia, 2 pages (Date Channel Catfish (Ictalurus punctatus ), Bluegill Sunfish (Lepomis Unknown). microchirus), and Crawfish (Procambarus spp.) (1997)pp. 237-243. Wright, Galen M. et al., Understory Vegetation Control to Establish Arif, Anwar et al., Lalang Grass Control with Low Spray Volume of Oak Regeneration, North Central Weed Control Conference Proceed Glyphosate Herbicide, Symposium in Weed Science (Biotrop Spe ings, Columbus, Ohio, vol. 38, 1983, p. 139. cial Publication) No. 24, pp. 317-324 (1986). Wyrill, J.B. et al., Glyphosate Toxicity to Common Milkweed and Arsenovic, M. et al., Brighton Crop Protection Conference Weeds Hemp Dogbane as Influenced by Surfactants, Weed Science, vol. 25. (1991), Weed Control on Railways in Yugoslavia, p. 1159. No. 3, pp. 275-287, May 1977. Chee, Y.K. etal. Sheep Grazing Reduces Chemical Weed Control in Yeiser, J.L., June, July and August Applications of Glyphosate Tank Rubber, pp. 120-123 (Date Unknown). Mixes for Site Preparation, Proceedings Southern Weed Sci. Soc. Chorbadian R. et al., Interaction between glyphosate and fluroxypyr (1991) San Antonio, TX, pp. 250-255. improve mallow control, Crop Protection, vol. 21 (2002) pp. 689 “Registered Pesticides 1992-1994” prepared by Pesticides Board 692. Malaysia, 3 pages. Daggett R. Howard et al., Long-Term Effects of Herbicide and Pre Crockett, Dinah, Grammatically Correct, Retrieved Feb. 27, 2012 commercial Thinning on Young Spruce-Fir Stands: The Austin Pond from http://www.uhv.edu/ac/newsletters/writing grammartip2006. Study, Silviculture Research, Cooperative Forestry Research Unit 08.29.htm, 2 pages. Annual Report 2001-2002, University of Maine, pp. 29-31. International Search Report dated Aug. 24, 2004 relating to Interna Harahap, Widjaya, The Study of Glyphosate and its Mixture in Con tional Application No. PCT/US2004/012368, 7 pages. trolling General Weeds in Rubber Planting Strips, Symposium in Statement of Grounds and Particulars in the Opposition of Australian Weed Science, BIOTROP Spec. Publ. No. 24 (1986), pp. 349-357. Patent Application No. 2004232335 dated Jun. 23, 2011, 12 pages. Holt, H. A. et al., Controlling Woody Plants with Wiping Application, Exhibit PMH-1 Resume of Phillip Maxwell Hay (Oct. 2011), 4 39th Annual Southern Weed Sci. Soc. Proceedings, Nashville, Ten pageS. nessee (1986), p. 364. Exhibit PMH-2 Federal Court of Australia, Practice Note CM 7, Howell, R.K. et al., Low Volume Foliar Applications of Triclopyr, Expert Witnesses in Proceedings in the Federal Court of Australia Picloram, Imazapyr and Glyphosate Mixtures for Rights-of-Way (Oct. 2011), 3 pages. Cleanup, Proceedings Southern Weed Science Society, Birmingham, Exhibit PMH-3—Glyphosate: A Unique Global Herbicide by John E. Alabama (1998), pp. 195-197. Franz, (p. 192) (1997), 4 pages. Jackson, Nelroy E. Control of Brush and Chaparral Species with Exhibit PMH-4 Glyphosate: A Unique Global Herbicide by John E. Glyphosate, 38th Annual California Weed Conference, Fresno, Cali Franz (pp. 187-193) (1997), 36 pages. fornia (1986), pp. 221-223. Exhibit PMH-5—Documentation regarding Roundup CT Herbicide Kay, S.H. et al. Effects of Tank Mixing Triclopyr Amine and by Monsanto, NRA Approval No. 31394/1102, (Jun. 2002) 16 pages. Glyphosate on Control of Alligatorweed, Proc. Southern Weed Sci Exhibit PMH-6—Documentation regarding Roundup PowerMax ence Society, Little Rock, Arkansas (1992), p. 291. Herbicide by Monsanto (bears the date of Nov. 2002), 14 pages. Label and Material Safety Data Sheet for Eclipse Glyphosate Toler Exhibit PMH-7—Documentation regarding Roundup Max Group M ant Canola Herbicide Tank-Mix (2002) Dow AgroSciences, 12 Herbicide by Monsanto (Date Unknown), 20 pages. pageS. Exhibit PMH-8 WO 01/89302 published on Nov. 29, 2001 (Appli Lawlor, Frances M. et al., Response of Swallow-wort to herbicides cant: Monsanto Technology, LLC), 367 pages. (2001), Weed Science, vol. 50, No. 2, Abstract only, 1 page. Exhibit PMH-9—article entitled Glyphosate Toxicity to Common Lawrie, J. et al., Effects of herbicide mixtures and additives on Milkweed and Hemp Dogband as Influenced by Surfactants by J.B. Rhododendron ponticum, Weed Research, vol. 33, pp. 25-34 (1993). Wyrill, Weed Science, vol. 25, Issue 3 (May 1977), 14 pages. Leys, A.R. et al., Evaluation of herbicides for control of Summer Exhibit PMH-10 Product Guide Book 2000, Dow AgroSciences growing weeds on fallows in South-eastern Australia, Austr. J. (2000), 44 pages. Experim. Agricult. (1990) vol. 30, No. 2, pp. 271-278. Exhibit PMH-11—Documentation on Nufarm Invader 600 Herbi Little, Keith et al., Control of Eucalyptus grandis cut stumps, ICFR cide regarding Directions for Use (bears the date of Feb. 11, 2000), 5 Bulletin Series No. Feb. 1998, 16 pages. pageS. Little, Keith M. et al., First rotation Eucalyptus macarthurii cut stump Exhibit PMH-12—Documentation on Generex Triclopyr 600 Herbi control in KwaZulu-Natal, South Africa, South African Forestry cide (bears the date of Jun. 14, 2000), 17 pages. Journal No. 207, pp. 15-20, Jul. 2006. Exhibit PMH-13—Documentation on Garlon 4 Specialty Herbicide Little, Keith et al., The killing of Eucalyptus grandis multiple-stem (bears the date of Sep. 8, 1995), 16 pages. cut-stumps in the Karkloof Project, ICFR Bulletin Series No. Mar. Exhibit PMH-14—Documentation on Garlon 3A, EPA Reg. No. 2000, 6 pages. 62719-37 (bears the year 1996), 16 pages. US 8,586,504 B2 Page 3

(56) References Cited Milne, B., 1990 Results, Weed Research & Demonstration Unit, Agricultural Research & Veterinary Centre, NSW Agriculture & OTHER PUBLICATIONS Fisheries, 3 pages. Milne, B., 1992 Results, Weed Research & Demonstration Unit, Exhibit PMH-15—Documentation on Roundup CT Broadacre Her bicide (Mar. 31, 2000), 8 pages. Agricultural Research & Veterinary Centre, NSW Agriculture, 11 Exhibit PMH-16—Material Safety Data Sheet for Scotts Australia pageS. Pty. Ltd. (bears the date of Apr. 15, 2004), 5 pages. Roundup CT Broadacre Herbicide, Pubic Chemical Registration Vermeulen, J.D., et al., A Guide to the Use of Herbicides, 1993, 14th Information System, http://services.apVma.gov .au Pubcris Ed., pp. 112-123. WebClientldetails.do?view=summary&pcode=316..., downloaded Milne, B., 1987 Results, Weed Research & Demonstration Unit, Jun. 20, 2013, 6 pages. Agricultural Research & Veterinary Centre, Department of Agricul ture, New South Wales, 4 pages. Lontrel Herbicide Product Label, N.R.A. Label No. 31635/1102, The Herbicide Glyphosate, 1985, Grossbard and Atkinson, Eds. approved Nov. 14, 2002, 12 pages. Butterworth & Co. (Publishers) Ltd., p. 223. Statutory Declaration of Phillip Maxwell Hay, filed Jun. 25, 2013 in Chambers, A., “Field Crop Herbicide Guide 1997-1998”, Institute Australian Patent Application No. 2004232335, 35 pages. for Integrated Agricultural Development, RMB 1145, Rutherglen, 3685, Kondinin Group, Publisher, pp. 337-338. * cited by examiner US 8,586,504 B2 1. 2 HERBICIDAL COMPOSITIONS CONTAINING sate is in a slight excess, or triclopyr is in excess), and/or (ii) GLYPHOSATE AND A PYRONE ANALOG not utilized a surfactant therein. For example, R. K. Howell et al. (Southern Weed Science REFERENCE TO RELATED APPLICATIONS Society Proceedings, 195-197 (1998)) disclose the prepara tion of a tank mixture containing a Surfactant TL90, Roundup This application is a continuation of U.S. application Ser. ProR) and GarlonTM4, the glyphosate (in Roundup ProR) and No. 10/829,572 (filed on Apr. 22, 2004), and claims priority triclopyr (in GarlonTM4) being present in an apparent weight from U.S. Provisional Application Ser. No. 60/496,031 (filed ratio of approximately 1.3:1, respectively. on Apr. 22, 2003), and U.S. Provisional Patent Application G. M. Wright et al. (North Central Weed Control Confer 10 ence Proceedings, vol. 38, 139 (1983)) disclose the prepara Ser. No. 60/552,065 (filed Mar. 10, 2004), the entire contents tion of a tank mixture of glyphosate and triclopyr in the of which are incorporated herein by reference. apparent absence of a surfactant, the glyphosate and triclopyr, respectively, being present in an apparent weight ratio of BACKGROUND OF THE INVENTION approximately 1.5:1. 15 M. L. McCormacket al. (Northeastern Weed Society Pro The present invention relates generally to herbicidal com ceedings, vol. 36,209-214 (1982)) disclose the preparation of positions or formulations, and to methods of using Such com a tank mixture of glyphosate and triclopyr in the apparent positions to kill, or control the growth and proliferation of absence of a Surfactant, the glyphosate and triclopyr, respec unwanted plants. In particular, the present invention relates to tively, being present in an apparent weight ratio of approxi herbicidal compositions, as well as their methods of use, mately 1.4:1. which comprise N-phosphonomethylglycine, or a herbicidal J. Lawrie et al. (Weed Research, vol. 33, 25-34, (1993) derivative thereof, and a pyridine analog, or a herbicidal appear to disclose the preparation of a tank mixture of gly derivative thereof, optionally with one or more suitable sur phosate, triclopyr and a surfactant-containing mixture, factants. Such compositions cause early visual symptoms of wherein the glyphosate and triclopyr, respectively, appear to treatment and/or enhanced effectiveness or control when 25 be present in a weight ratio of approximately 1.67:1. applied to the foliage of plants. W. Harahap et al. (Biotrop Special Publication, no. 24. Herbicidal compositions comprising the herbicide 317-24 (1986)) disclose the preparation of tank mixtures of N-phosphonomethylglycine or derivatives thereof ("glypho glyphosate and triclopyr or picloram, in the apparent absence sate'), are useful for Suppressing the growth of or killing, of a Surfactant. In the tank mixtures, glyphosate and triclopyr unwanted plants such as grasses, weeds and the like. Glypho 30 are, respectively, present in an apparent weight ratio of sate typically is applied to the foliage of the target plant. After approximately 9.5:1 or 11.5:1, while glyphosate and piclo application the glyphosate is absorbed by the foliar tissue of ram are present in an apparent weight ratio of approximately the plant and translocated throughout the plant. Glyphosate 7.7:1. noncompetitively blocks an important biochemical pathway S. H. Kay et al. (Southern Weed Science Society Proceed which is common to virtually all plants, but which is absent in 35 ings, 291 (1992)) disclose the preparation of a tank mixture of animals. Although glyphosate is very effective in killing or glyphosate and triclopyr in the apparent absence of a Surfac controlling the growth of unwanted plants, the uptake (i.e., tant, the glyphosate and triclopyr, respectively, being present absorption) of glyphosate by the plant foliar tissue and trans in a weight ratio of approximately 1:1. location of glyphosate throughout the plant is relatively slow. A Roundup Pro(R) Supplemental Label (for application in Visual symptoms that a plant has been treated with glypho 40 California using a helicopter. EPA Reg. No. 524-475, Mon sate may not appear until one week or more after treatment. santo Company (1996)), discloses the optional preparation of Compositions comprising glyphosate may be formulated a tank mixture of Roundup ProR) and GarlonTM 4 in varying with one or more surfactants to enhance their effectiveness for weight ratios of glyphosate and triclopyr, respectively, as well foliar application. When water is added to a composition as varying concentrations related thereto. formulated with Surfactants, the resulting sprayable compo 45 Tank mixtures require the user to purchase and store each sition more easily and effectively covers the foliage (e.g., the herbicide used in the mixture separately, until the actual leaves or other photosynthesizing organs) of plants. Glypho preparation of such mixtures in the field. The user must also sate salts, for example, have been formulated with Surfactants measure out varying amounts of each herbicide used in the Such as polyoxyalkylene-type Surfactants including, among mixture. Therefore, a pre-packaged mixture (i.e., a concen other Surfactants, polyoxyalkylene alkylamines. Commercial 50 trate) which already contains the desired herbicides in a formulations of glyphosate herbicide marketed under the single container may be desirable in some instances. How trademark ROUNDUPR) have been formulated by Monsanto ever, concentrates may be difficult to prepare, for example with Such a polyoxyalkylene alkylamine, in particular a poly when one of the herbicides is not soluble or miscible with the oxyethylene tallowamine. same desired solvent (e.g., water). As a result of the somewhat slow development of visual 55 The solubility or miscibility problems sometimes encoun symptoms that may result when glyphosate is utilized alone, tered with concentrates may be overcome by preparing a formulations or compositions containing glyphosate and concentrated emulsion formulation. A concentrated emulsion another herbicide have been Suggested, in an attempt to formulation consists of two phases and is a dispersion of one achieve both early visual symptoms of plant treatment and immiscible liquid (i.e., the discontinuous phase) in a second prolonged control of the plant. For example, Some have Sug 60 liquid (i.e., the continuous phase). If the continuous phase is gested using a tank mix composition containing glyphosate water, the emulsion is an oil-in-water type emulsion and the and a contact herbicide. Such as a pyridine analog like triclo water-immiscible liquid or solution may be referred to as the pyr (i.e., (3,5,6-trichloro-2-pyridinyl)oxyacetic acid) or a “oil” phase (regardless of its composition). In a concentrated herbicidal derivative thereof. However, to-date, such tank emulsion formulation, the active ingredient may be dissolved mixes have generally (i) employed relatively low weight 65 in an organic solvent along with added emulsifiers and/or ratios of glyphosate to, for example, triclopyr (wherein gly dispersants. When the concentrate is added to water, the phosate and triclopyr are present in equal amounts, glypho active ingredient becomes dispersed throughout the water. US 8,586,504 B2 3 4 Such a concentrate, in the form of a microemulsion, was for application to the foliage of a plant. The concentrate prepared in U.K. Patent Application No. GB 2267 825A, comprises glyphosate, or a herbicidal derivative thereof, a using a slight excess of the isopropylamine salt of glyphosate pyridine analog selected from the group consisting of triclo relative to the butoxyethyl ester of triclopyr (weight ratio of pyr, clopyralid, dithiopyr, thiazopyr and picloram, or a herbi glyphosate to triclopyr approximately 1.6:1), and a high load 5 cidal derivative thereof, in a concentration ranging from or amount of triclopyr and two ethoxylated cocoamine Sur about 1 gram to 99 grams (acid equivalent basis) per liter, and factants, EthomeenTM C-15 and C-25 (approximately 100 g/L at least one surfactant, wherein (i) the glyphosate (acid triclopyr and approximately 285 g/L total Surfactant). equivalent basis) and the pyridine analog (acid equivalent basis) are present in a weight ratio of at least 1:1, glyphosate SUMMARY OF THE INVENTION 10 being in excess, and (ii) when the glyphosate is predomi nantly in the form of a salt, said salt is selected from the group Briefly, therefore, the present invention is directed to an consisting of a sodium salt, an ammonium salt, an alkylam aqueous herbicidal liquid concentrate, which may be diluted monium salt, a C- alkanolammonium salt, a di-ammonium with water to provide an aqueous herbicidal application mix salt, an alkylamine salt, a C- alkanolamine salt, an alkyl ture for application to the foliage of a plant. The concentrate 15 Sulfonium salt, a Sulfoxonium salt, and combinations thereof. comprises glyphosate, or a herbicidal derivative thereof, in a The present invention is still further directed to an aqueous concentration of at least about 50 grams acid equivalent per herbicidal liquid concentrate, which may be diluted with liter, a pyridine analog selected from the group consisting of water to provide an aqueous herbicidal application mixture triclopyr, clopyralid, dithiopyr, thiazopyr and picloram, or a for application to the foliage of a plant. The concentrate herbicidal derivative thereof, and at least one surfactant, comprises glyphosate, or a herbicidal derivative thereof, a wherein (i) the glyphosate (acid equivalent basis) and the pyridine analog selected from the group consisting of triclo pyridine analog (acid equivalent basis) are present in a weight pyr, clopyralid, dithiopyr, thiazopyr and picloram, or a herbi ratio of at least 1.7:1, and (ii) when the glyphosate is predomi cidal derivative thereof, and at least one surfactant, wherein nantly in the form of a salt, said salt is selected from the group (i) the glyphosate (acid equivalent basis) and the pyridine consisting of a sodium salt, an ammonium salt, an alkylam 25 analog (acid equivalent basis) are present in a weight ratio of monium salt, a C- alkanolammonium salt, a di-ammonium at least 1:1, (ii) the glyphosate (acid equivalent basis) and the salt, an alkylamine salt, a C- alkanolamine salt, an alkyl Surfactant are present in a weight ratio of at least 1:1, wherein Sulfonium salt, a Sulfoxonium salt, and combinations thereof. glyphosate is in excess in both instances, and (iii) when the The present invention is further directed to an aqueous glyphosate is predominantly in the form of a salt, said salt is herbicidal liquid concentrate, which may be diluted with 30 selected from the group consisting of a sodium salt, an ammo water to provide an aqueous herbicidal application mixture nium salt, an alkylammonium salt, a C- alkanolammonium for application to the foliage of a plant. The concentrate salt, a di-ammonium salt, an alkylamine salt, a C- alkano comprises glyphosate, or a herbicidal derivative thereof, in a lamine salt, an alkylsulfonium salt, a Sulfoxonium salt, and concentration of at least about 50 grams acid equivalent per combinations thereof. liter, a pyridine analog selected from the group consisting of 35 The present invention is still further directed to an aqueous triclopyr, clopyralid, dithiopyr, thiazopyr and picloram, or a herbicidal liquid concentrate, which may be diluted with herbicidal derivative thereof, and at least one surfactant, water to provide an aqueous herbicidal application mixture wherein (i) the glyphosate (acid equivalent basis) and the for application to the foliage of a plant. The concentrate pyridine analog (acid equivalent basis) are present in a weight comprises glyphosate, or a herbicidal derivative thereof, and ratio ranging from at least 1.7:1 to less than about 32:1, and 40 a pyridine analog selected from the group consisting of tri (ii) when the glyphosate is predominantly in the form of a salt, clopyr, clopyralid, dithiopyr, thiazopyr and picloram, or a said salt is selected from the group consisting of a sodium salt, herbicidal derivative thereof, wherein the glyphosate (acid an ammonium salt, an alkylammonium salt, a C- alkano equivalent basis) and the pyridine analog (acid equivalent lammonium salt, a di-ammonium salt, an alkylamine salt, a basis) are present in a weight ratio of at least 1:1, glyphosate C. alkanolamine salt, an alkylsulfonium salt, a Sulfoxo 45 being in excess, and further wherein (i) the pyridine analog or nium salt, and combinations thereof. a herbicidal derivative thereof is presentata concentration of The present invention is still further directed to an aqueous not greater than 99 grams (acid equivalent) per liter, and (ii) herbicidal liquid concentrate, which may be diluted with when the glyphosate is predominantly in the form of a salt, water to provide an aqueous herbicidal application mixture said salt is selected from the group consisting of a sodium salt, for application to the foliage of a plant. The concentrate 50 an ammonium salt, an alkylammonium salt, a C- alkano comprises glyphosate, or a herbicidal derivative thereof, a lammonium salt, a di-ammonium salt, an alkylamine salt, a pyridine analog selected from the group consisting of triclo C. alkanolamine salt, an alkylsulfonium salt, a Sulfoxo pyr, clopyralid, dithiopyr, thiazopyr and picloram, or a herbi nium salt, and combinations thereof. cidal derivative thereof, and at least one Surfactant in a con The present invention is still further directed to an aqueous centration ranging from about 1 grams to 283 grams per liter, 55 herbicidal liquid concentrate, which may be diluted with wherein (i) the glyphosate (acid equivalent basis) and the water to provide an aqueous herbicidal application mixture pyridine analog (acid equivalent basis) are present in a weight for application to the foliage of a plant. The concentrate ratio of at least 1:1, glyphosate being in excess, and (ii) when comprises glyphosate, or a herbicidal derivative thereof, and the glyphosate is predominantly in the form of a salt, said salt a pyridine analog, or a herbicidal derivative thereof, wherein is selected from the group consisting of a sodium salt, an 60 the glyphosate (acid equivalent basis) and the pyridine analog ammonium salt, an alkylammonium salt, a C- alkanolam (acid equivalent basis) are present in a weight ratio of at least monium salt, a di-ammonium salt, an alkylamine salt, a C 1:1, glyphosate being in excess, and further wherein (i) the alkanolamine salt, an alkylsulfonium salt, a Sulfoxonium salt, glyphosate (acid equivalent basis) or herbicidal derivative and combinations thereof. thereof is present at a concentration of not greater than 165 The present invention is still further directed to an aqueous 65 grams (acid equivalent) per liter, and (ii) when the glyphosate herbicidal liquid concentrate, which may be diluted with is predominantly in the form of a salt, said salt is selected from water to provide an aqueous herbicidal application mixture the group consisting of a sodium salt, an ammonium salt, an US 8,586,504 B2 5 6 alkylammonium salt, a C- alkanolammonium salt, a di ammonium salt, an alkylammonium salt, a C- alkanolam ammonium salt, an alkylamine salt, a C- alkanolamine salt, monium salt, a di-ammonium salt, an alkylamine salt, a C an alkylsulfonium salt, a Sulfoxonium salt, and combinations alkanolamine salt, an alkylsulfonium salt, a Sulfoxonium salt, thereof. and combinations thereof. The present invention is still further directed to an aqueous The present invention is still further directed to an aqueous herbicidal liquid concentrate which may be diluted with herbicidal composition useful for killing or controlling the water to provide an aqueous herbicidal application mixture growth of unwanted plants. The composition comprises gly for application to the foliage of a plant. The concentrate phosate, or a herbicidal derivative thereof, a pyridine analog comprises at least one glyphosate Salt predominantly in the selected from the group consisting of triclopyr, clopyralid, form of potassium glyphosate, monoethanolamine glypho 10 dithiopyr, thiazopyr and picloram, or a herbicidal derivative sate, or a mixture thereof a pyridine analog selected from the thereof, and at least one surfactant, wherein (i) the Surfactant group consisting of triclopyr, clopyralid, fluoroxypyr, dithi concentration is not greater than 3.9 grams per liter, (ii) gly opyr, thiazopyr and picloram, or a herbicidal derivative phosate (acid equivalent basis) and the pyridine analog (acid thereof, and, at least one surfactant in a concentration less equivalent basis) are present in a weight ratio of at least 3:1, than 20 grams per liter; wherein the glyphosate (acid equiva 15 and (iii) when the glyphosate is predominantly in the form of lent basis) and the pyridine analog (acid equivalent basis) are a salt, said salt is selected from the group consisting of a present in a weight ratio of at least 1:1, glyphosate being in Sodium salt, an ammonium salt, an alkylammonium salt, a CXCSS. C. alkanolammonium salt, a di-ammonium salt, an alky The present invention is further directed to an aqueous lamine salt, a C- alkanolamine salt, an alkylsulfonium salt, herbicidal liquid concentrate, which may be diluted with a Sulfoxonium salt, and combinations thereof. water to provide an aqueous herbicidal application mixture The present invention is still further directed to an aqueous for application to the foliage of a plant. The concentrate herbicidal composition useful for killing or controlling the comprises glyphosate, or a herbicidal derivative thereof, in a growth of unwanted plants. The composition comprises gly concentration of less than 65 grams acid equivalent per liter, phosate, or a herbicidal derivative thereof, a pyridine analog, picloram, or a herbicidal derivative thereof, and at least one 25 or a herbicidal derivative thereof, and at least one surfactant, Surfactant, wherein (i) the glyphosate (acid equivalent basis) wherein (i) the Surfactant concentration is not greater than 6.6 and the picloram (acid equivalent basis) are present in a grams per liter, (ii) glyphosate (acid equivalent basis) and the weight ratio of at least 1:1, with glyphosate being in excess. pyridine analog (acid equivalent basis) are present in a weight Optionally, when the glyphosate is predominantly in the form ratio of at least 5:1, and (iii) when the glyphosate is predomi of a salt, said salt may be selected from the group consisting 30 nantly in the form of a salt, said salt is selected from the group of a sodium salt, an ammonium salt, an alkylammonium salt, consisting of a sodium salt, an ammonium salt, an alkylam a C- alkanolammonium salt, a di-ammonium salt, an alky monium salt, a C- alkanolammonium salt, a di-ammonium lamine salt, a C- alkanolamine salt, an alkylsulfonium salt, salt, an alkylamine salt, a C- alkanolamine salt, an alkyl a Sulfoxonium salt, and combinations thereof. Sulfonium salt, a Sulfoxonium salt, and combinations thereof. The present invention is still further directed to a method of 35 The present invention is still further directed to an aqueous killing or controlling weeds or unwanted vegetation. The herbicidal composition useful for killing or controlling the method comprises diluting one of the preceding liquid con growth of unwanted plants. The composition comprises gly centrates in a convenient amount of water to form an appli phosate, or a herbicidal derivative thereof, a pyridine analog, cation mixture, and then applying a herbicidally effective or a herbicidal derivative thereof, and at least one surfactant, amount of the application mixture to the foliage of the weeds 40 wherein (i) the Surfactant concentration is not greater than 9.3 or unwanted vegetation. grams per liter, (ii) glyphosate (acid equivalent basis) and the The present invention is still further directed to an aqueous pyridine analog (acid equivalent basis) are present in a weight herbicidal composition useful for killing or controlling the ratio of at least 7:1, and (iii) when the glyphosate is predomi growth of unwanted plants. The composition comprises gly nantly in the form of a salt, said salt is selected from the group phosate, or a herbicidal derivative thereof, a pyridine analog, 45 consisting of a sodium salt, an ammonium salt, an alkylam or a herbicidal derivative thereof, and at least one surfactant, monium salt, a C- alkanolammonium salt, a di-ammonium wherein (i) the glyphosate (acid equivalent basis) and the salt, an alkylamine salt, a C- alkanolamine salt, an alkyl pyridine analog (acid equivalent basis) are present in a weight Sulfonium salt, a Sulfoxonium salt, and combinations thereof. ratio of at least 7.6:1, and (ii) when the glyphosate is predomi The present invention is still further directed to an aqueous nantly in the form of a salt, said salt is selected from the group 50 herbicidal composition useful for killing or controlling the consisting of a sodium salt, an ammonium salt, an alkylam growth of unwanted plants. The composition comprises gly monium salt, a C- alkanolammonium salt, a di-ammonium phosate or a herbicidal derivative thereof, apyridine analog or salt, an alkylamine salt, a C- alkanolamine salt, an alkyl a herbicidal derivative thereof, and at least one surfactant, Sulfonium salt, a Sulfoxonium salt, and combinations thereof. wherein either (i) the glyphosate concentration (acid equiva The present invention is still further directed to an aqueous 55 lent basis) is not greater than 16.2 grams per liter, and gly herbicidal composition useful for killing or controlling the phosate (acid equivalent basis) and the pyridine analog (acid growth of unwanted plants. The composition comprises gly equivalent basis) are presentina weight ratio of at least 4:1, or phosate, or a herbicidal derivative thereof, a pyridine analog (ii) the glyphosate concentration (acid equivalent basis) is not selected from the group consisting of triclopyr, clopyralid, greater than 23.8 grams per liter, and glyphosate (acid equiva dithiopyr, thiazopyr and picloram, or a herbicidal derivative 60 lent basis) and the pyridine analog (acid equivalent basis) are thereof, in a concentration of not greater than 3.9 grams (acid present in a weight ratio of at least 6:1, and further when the equivalent basis) per liter, and at least one Surfactant, wherein glyphosate is predominantly in the form of a salt, said salt is (i) the glyphosate (acid equivalent basis) and the pyridine selected from the group consisting of a sodium salt, an ammo analog (acid equivalent basis) are present in a weight ratio of nium salt, an alkylammonium salt, a C- alkanolammonium at least about 1:1, glyphosate being in excess, and (ii) when 65 salt, a di-ammonium salt, an alkylamine salt, a C- alkano the glyphosate is predominantly in the form of a salt, said salt lamine salt, an alkylsulfonium salt, a Sulfoxonium salt, and is selected from the group consisting of a sodium salt, an combinations thereof. US 8,586,504 B2 7 8 The present invention is still further directed to an aqueous The present invention is still further directed to a method of herbicidal composition useful for killing or controlling the killing or controlling weeds or unwanted vegetation. The growth of unwanted plants. The concentrate comprises at method comprises diluting or dissolving the previously least one glyphosate salt predominantly in the form of potas described solid particulate concentrate in a convenient sium glyphosate, monoethanolamine glyphosate, or a mix amount of water to form an application mixture, and then ture thereof, and a pyridine analog selected from the group applying a herbicidally effective amount of the application consisting of triclopyr, clopyralid, fluoroxypyr, dithiopyr, mixture to the foliage of the weeds or unwanted vegetation. thiazopyr and picloram, or a herbicidal derivative thereof; The present invention is still further directed to one or more wherein (i) the glyphosate salt is present in a concentration of the previously noted methods for killing or controlling the less than 180grams acid equivalent per liter and the glypho 10 growth of unwanted plants which comprises contacting the sate salt (acid equivalent basis) and the pyridine analog (acid foliage of said plants with Such an aqueous herbicidal com equivalent basis) are present in a weight ratio of at least 1:1, position, wherein said herbicidal composition is brought into glyphosate being in excess; (ii) the glyphosate salt is present contact with, or applied to, said foliage using means other in a concentrationless than 240 grams acid equivalent per liter 15 than a helicopter. and the glyphosate salt (acid equivalent basis) and the pyri The present invention is still further directed to a method of dine analog (acid equivalent basis) are present in a weight killing or controlling weeds or unwanted plants. The method ratio of at least 2:1; (iii) the glyphosate salt is present in a comprises diluting an aqueous herbicidal concentrate com concentration less than 270 grams acid equivalent per liter positioninanamount of water to forman application mixture; and the glyphosate salt (acid equivalent basis) and the pyri and, applying a herbicidally effective amount of the applica dine analog (acid equivalent basis) are present in a weight tion mixture to foliage of the weeds or unwanted plants, ratio of at least 3:1; (iv) the glyphosate salt is present in a wherein the weeds or unwanted plants comprise poison ivy, concentration less than 288 grams acid equivalent per liter poison oak, kudzu, multiflora rose, golden rod, blue fescue, and the glyphosate salt (acid equivalent basis) and the pyri red maple, and/or red oak, and the aqueous herbicidal con dine analog (acid equivalent basis) are present in a weight 25 centrate composition comprises glyphosate or a herbicidal ratio of at least 4:1; (v) the glyphosate salt is present in a derivative thereof; a pyridine analog selected from the group concentration less than 300 grams acid equivalent per liter consisting of triclopyr, clopyralid, dithiopyr, thiazopyr and and the glyphosate salt (acid equivalent basis) and the pyri picloram, or a herbicidal derivative thereof; and, at least one dine analog (acid equivalent basis) are present in a weight Surfactant. ratio of at least 5:1, (vi) the glyphosate salt is present in a 30 The present invention is still further directed to one or more concentration less than 308 grams acid equivalent per liter of the previously described aqueous herbicidal liquid concen and the glyphosate salt (acid equivalent basis) and the pyri trates, aqueous herbicidal compositions, herbicidal particu dine analog (acid equivalent basis) are present in a weight late solid concentrates, and methods for the use thereof, ratio of at least 6:1, (vii) the glyphosate salt is present in a wherein said pyridine analogistriclopyr, a derivative thereof, concentration less than 315 grams acid equivalent per liter 35 or some combination which includes triclopyr. and the glyphosate salt (acid equivalent basis) and the pyri The present invention is still further directed to one or more dine analog (acid equivalent basis) are present in a weight of the previously described aqueous herbicidal liquid concen ratio of at least 7:1, (viii) the glyphosate salt is present in a trates, aqueous herbicidal compositions, herbicidal particu concentration less than 320 grams acid equivalent per liter late solid concentrates, and methods for the use thereof, and the glyphosate salt (acid equivalent basis) and the pyri 40 wherein said pyridine analog is clopyralid, a derivative dine analog (acid equivalent basis) are present in a weight thereof, or some combination which includes clopyralid. ratio of at least 8:1; (ix) the glyphosate salt is present in a The present invention is still further directed to one or more concentration less than 324 grams acid equivalent per liter of the previously described aqueous herbicidal liquid concen and the glyphosate salt (acid equivalent basis) and the pyri trates, aqueous herbicidal compositions, herbicidal particu dine analog (acid equivalent basis) are present in a weight 45 late solid concentrates, and methods for the use thereof, ratio of at least 9:1; or (X) the glyphosate salt is present in a wherein said pyridine analog is dithiopyr, a derivative thereof, concentration less than 326 grams acid equivalent per liter or some combination which includes dithiopyr. and the glyphosate salt (acid equivalent basis) and the pyri The present invention is still further directed to one or more dine analog (acid equivalent basis) are present in a weight of the previously described aqueous herbicidal liquid concen ratio of at least 10:1. 50 trates, aqueous herbicidal compositions, herbicidal particu The present invention is still further directed to a method late solid concentrates, and methods for the use thereof, for killing or controlling the growth of unwanted plants. The wherein said pyridine analog is thiazopyr, a derivative method comprises contacting the foliage of said plants with a thereof, or some combination which includes thiazopyr. herbicidally effective amount of one of the previously The present invention is still further directed, where appro described aqueous herbicidal compositions. 55 priate, to one or more of the previously described aqueous The present invention is still further directed to a herbicidal herbicidal liquid concentrates, aqueous herbicidal composi particulate solid concentrate which may be dissolved or dis tions, herbicidal particulate solid concentrates, and methods persed in water to provide an aqueous herbicidal application for the use thereof, wherein said pyridine analog is picloram, mixture for application to the foliage of a plant. The solid a derivative thereof, or some combination which includes concentrate comprises glyphosate, or a herbicidal derivative 60 picloram. thereof, and a pyridine analog, or a herbicidal derivative The present invention is still further directed, where appro thereof, wherein a weight ratio (a.e. basis) of glyphosate to priate, to one or more of the previously described aqueous the pyridine analog is at least about 1:1, glyphosate being in herbicidal liquid concentrates, aqueous herbicidal composi excess, and further wherein when the glyphosate is predomi tions, herbicidal particulate solid concentrates, and methods nantly in the form of a salt. Optionally, one or more Surfac 65 for the use thereof, wherein said pyridine analog is fluoroxy tants may be present in the herbicidal particulate solid con pyr, a derivative thereof, or some combination which includes Centrate. fluoroxypyr. US 8,586,504 B2 10 The present invention is still further directed, where appro ammonium salt, di-ammonium salt, sodium salt, monoetha priate, to one or more of the previously described aqueous nolamine salt, and trimethylsulfonium salt, as well as com herbicidal liquid concentrates, aqueous herbicidal composi binations thereof. For still other preferred embodiments, gly tions, herbicidal particulate solid concentrates, and methods phosate is predominantly in the form of a salt other than a for the use thereof, wherein said pyridine analog is a combi potassium salt or a monoethanolamine or monoethanolam nation or mixture of one or more of triclopyr, fluoroxypyr, monium salt; that is, in an alternative preferred embodiment dithiopyr, thiazopyr, picloram, or derivatives thereof. glyphosate is a salt predominantly in the form of the isopro The present invention is still further directed, where appro pylamine salt, the ammonium salt, the di-ammonium salt, the priate, to one or more of the previously described aqueous Sodium salt, the trimethylsulfonium salt, or some combina herbicidal liquid concentrates, aqueous herbicidal composi 10 tion thereof. tions, herbicidal particulate solid concentrates, and methods The herbicidal properties of N-phosphonomethylglycine for the use thereof, wherein said pyridine analog is a combi and its derivatives were first discovered by Franz, then dis nation or mixture of triclopyr and clopyralid, or derivatives closed and patented in U.S. Pat. No. 3,799,758, issued Mar. thereof. 26, 1974. A number of herbicidal salts of N-phosphonometh The present invention is still further directed, where appro 15 priate, to one or more of the previously described aqueous ylglycine were patented by Franz in U.S. Pat. No. 4,405.531. herbicidal liquid concentrates, aqueous herbicidal composi issued Sep. 20, 1983. The disclosures of both of these patents tions, herbicidal particulate solid concentrates, and methods are hereby incorporated by reference. for the use thereof, wherein said pyridine analog is a combi Various salts of N-phosphonomethylglycine are commer nation or mixture of one or more of triclopyr, clopyralid, cially significant, in part because they are water Soluble. fluoroxypyr, or derivatives thereof. Many of the salts listed herein are highly water soluble, thereby allowing for highly concentrated Solutions that can be DETAILED DESCRIPTION OF THE INVENTION diluted at the site of use. In accordance with the methods of this invention, as they pertain to glyphosate herbicide, a solu According to the present invention, coherbicidal composi 25 tion containing a herbicidally effective amount of glyphosate, tions or formulations containing glyphosate or a derivative and other components as described elsewhere herein (e.g., a thereof, a pyridine analog (e.g., triclopyr, clopyralid, flu pyridine analog, and optionally a surfactant), is applied to the oroxypyr, dithiopyr, thiazopyr, picloram, etc., or a combina foliage of plants. tion thereof) or a derivative thereof, and optionally a suitable A pyridine analog or derivative thereof (i.e., an acid, a salt Surfactant, are provided that are advantageous for a number of 30 or an ester form thereof). Such as one or more of those dis reasons, including rapid uptake by the target plant, early closed in U.S. Pat. No. 4,692.184 (which is incorporated in its visual symptoms of plant treatment, and control of a broad spectrum of plant species, as well as enhanced, more consis entirety herein by reference for all relevant purposes), is tent control of unwanted plants. Accordingly, in at least some another component of the composition of the present inven embodiments, lower application rates may potentially be 35 tion. In this regard it is to be noted that the phrase "pyridine used for the pyridine analog and/or the Surfactant(s) applied, analogs, as well as variations thereof, is intended to gener ally refer to a class of herbicides that includes, for example: without a loss of effectiveness of plant control. triclopyr (i.e., (3.5,6-trichloro-2-pyridinyl)oxyacetic acid), I. GLYPHOSATE AND PYRIDINEANALOG clopyralid (i.e., 3,6-dichloro-2-pyridine carboxylic acid), flu COHEREBICIDES 40 oroxypyr (i.e., (4-amino-3,5-dichloro-6-fluoro-pyridyl)oxy acetic acid), dithiopyr (i.e., S.S.-dimethylester-2-(difluorom A. Coherbicide Combinations and Forms ethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridine The compositions or formulations of the present invention dicarbothioic acid), thiazopyr (i.e., methyl 2-(difluorom comprise at least two herbicides, and optionally at least one ethyl)-5-(4,5-dihydro-2-thiazolyl)-4-(2-methylpropyl)-6- Surfactant. A first component of the compositions of the 45 (trifluoromethyl)-3-pyridine carboxylate), and picloram (i.e., present invention may be, for example, N-phosphonometh 4-amino-3,5,6-trichloropicolinic acid), as well as derivatives ylglycine (glyphosate'), a salt or adduct thereof, or a com thereof, in all of their various forms, including for example pound which is converted to glyphosate in plant tissues or the acid, the salt (e.g., amine salt, Such as monoethanolamine which otherwise provides glyphosate ion. In this regard it is to or triethylamine), and the ester (e.g., butoxyethyl ester). Such be noted that the term "glyphosate.” when used herein, is to be 50 compounds may be characterized, in one aspect of the present understood to encompass such derivatives unless the context invention, by the rapid symptomology and more consistent requires otherwise. control they impart. Glyphosate salts that can be used according to this inven In this regard it is to be noted that the present invention tion include but are not restricted to, for example, alkali metal encompasses essentially any formulation disclosed herein salts, for example sodium and potassium salts, ammonium 55 (e.g., concentrate, Solid or tank mix) which comprises gly salts, alkylammonium salts (e.g., C. alkylammonium, or phosate and any one of triclopyr, clopyralid, fluoroxypyr, alternatively C. alkylammonium), alkanolammonium dithiopyr, thiazopyr, picloram, or a derivative thereof, as well salts (e.g., C-1 alkanolammonium, or alternatively Cs as any combination or mixture which includes any one, two, alkanolammonium), di-ammonium salts such as dimethy there, four, five or six of these pyridine analogs. Exemplary lammonium, alkylamine salts, for example dimethylamine 60 co-herbicidal combinations are set forth in greater detail in and isopropylamine salts, alkanolamine salts (e.g., C. Coherbicide Tables A-E, below (which illustrate that glypho alkanolamine, or alternatively C. alkanolamine), for sate, or one of its salts, can be combined with pyridine analog example ethanolamine salts, alkylsulfonium salts (e.g., C. herbicides to form a herbicidal composition comprising two alkylsulfonium, for example trimethylsulfonium salts), Sul to seven actives, wherein: G-glyphosate; Tr-triclopyr; foXonium salts, and mixtures or combinations thereof. For 65 C-clopyralid; F=fluoroxypyr; D-dithiopyr; Th=thiazopyr; Some preferred embodiments, preferred glyphosate salts P-picloram; and “Active No.' is a herbicide combination include for example the potassium salt, isopropylamine salt, reference number): US 8,586,504 B2

TABLE A TABLE D-continued Glyphosate in combination with One pyridine analog herbicide Glyphosate in combination with four pyridine analog herbicides Active No. Herbicides 5 Active No. Herbicides

1 G - Tr 49 G + Tr - C+D+F 2 G + C 50 G + Tr + C + Th + F 3 G - F 51 G + Tr + D + Th + F 4 G - D 52 G + P + C + D + Th 5 G+ Th 53 G + P + C+D+F 6 G - P 10 S4 G + P + C + Th + F 55 G + P + D + Th - F 56 G + C + D + Th + F

TABLE B Glyphosate in combination with two pyridine analog herbicides 15 TABLE E Active No. Herbicides Glyphosate in combination with five pyridine analog herbicides 7 G - Tr - P 8 G + Tr - C Active No. Herbicides 9 G + Tri-D 2O 10 G + Tr + Th 57 G + Tr + P + C + D + Th 11 G - Tr - F 58 G + Tr P + C+D+ F 12 G - P -- C 59 G + Tr + P + C + Th + F 13 G - P -- D 60 G + Tr + P + D + Th + F 14 G+P.+ Th 61 G + Tr + C + D + Th + F 15 G - P - F 25 62 G + P + C + D + Th + F 16 G + C + D 17 G + C + Th - 0 18 G + C + F In one preferred embodiment, the pyridine analog is 19 G + D + Th selected from the group consisting of triclopyr, clopyralid, 2O G + P F dithiopyr, thiazopyr, picloram, or some combination thereof. 21 G - Th-F 30 In an alternative preferred embodiment, the pyridine analogis selected from the group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr, or some combination thereof. In yet TABLE C another preferred embodiment, the pyridine analog is - - - - selected from the group consisting of triclopyr, clopyralid, Glyphosate in combination with three pyridine analog herbicides 35 dithiopyr, or some combination thereof. In yet another pre Active No. Herbicides ferred embodiment, the pyridine analog is selected from the group consisting of triclopyr, clopyralid, or a combination 22 G - Tr - P - C thereof. In yet another preferred embodiment, the pyridine 2423 G+G - TrTr+P.+ - P -- ThD analog is selected from the group consisting of triclopyr, 25 G - Tr - P - F 40 dithiopyr, thiazopyr, or some combination thereof. In yet 26 G + Tr - C + D another preferred embodiment, the pyridine analog is 5. : I -- -- th selected from the group consisting of triclopyr, clopyralid, 29 G f D Th fluoroxypyr, or some combination thereof. 30 G + Tr - D +F With respect to the ester and salt forms of the pyridine 31 G + Tr + Th + F 45 analogs or derivatives thereof of the present invention, it is to 32 G + P + C + D be noted that the present invention encompasses essentially 3. : R : : th any Such ester or salt known to one of ordinary skill in the art, 35 G - P -- D - Th or which may be prepared thereby using techniques known in 36 G - P -- D - F the art. Exemplary salts may include alkali metal salts, for 37 G+P.+ Th+ F 50 example sodium and potassium salts, ammonium salts, alky 3938 G + C + D +F+ Th 1 ammonium salts1 (e.g., CC-16 alkyIkV1 ammonium), aiKanolamIk 1 40 G + C + Th - F monium salts (e.g., C-1 alkanolammonium), di-ammonium 41 G + D + Th - F salts such as dimethylammonium, alkylamine salts, for example dimethylamine and isopropylamine salts, alkanola 55 mine salts, for example ethanolamine salts, alkylsulfonium salts (e.g., C. alkylsulfonium, for example trimethylsulfo TABLED nium salts), Sulfoxonium salts, and mixtures or combinations Glyphosate in combination with four pyridine analog herbicides thereof. B. Concentrations and Ratios Active No. Herbicides 60 The relative amounts of glyphosate and the pyridine analog 42 G + Tr P + C + D (e.g., triclopyr, clopyralid, fluoroxypyr, dithiopyr, thiazopyr, 43 G + Tr - P + C + Th picloram, etc., or a combination thereof) present in a contem 44 G + Tr P + C + F p lated herbicidal compositionp (i.e., a pparticulate Solid con 45 G + Tr - P + D + Th 46 G - Tr- P - D - F centrate, or liquid concentrate, or alternatively a ready-to-use, 47 G+ Tr+P.+ Th+ F 65 or tank-mix, composition) may vary depending upon many 48 G + Tr - C + D + Th factors, including for example the plant species to be con trolled and the method of application. Generally speaking, US 8,586,504 B2 13 14 however, the concentrations of these herbicides, and option per liter or less). The glyphosate concentration may therefore ally a surfactant and/or some other additive (as described range, for example, from about 100 to no greater than 160 elsewhere herein), in the herbicidal compositions of the grams per liter, or from about 110 to no greater than 150 invention is sufficient to provide at least about 70% control grams per liter. (as determined by means known in the art) within about 50 In still other embodiments (e.g., a ready-to-use composi days, preferably about 40 days, more preferably about 30 tion, also known and referred to herein as a tank mix compo days, still more preferably about 20 days, still more prefer sition), the glyphosate concentration may be less than about ably about 15 days, still more preferably about 10 days, still 50, preferably less than about 45, more preferably less than more preferably about 5 days, and even still more preferably about 40, still more preferably less than about 35, still more about 1 day, or less, after application of the composition to a 10 preferably less than about 30, or even still more preferably plant. In a more preferred embodiment, the concentration of less than about 25 grams (a.e.) per liter (e.g., about 2, about 4. these herbicides, and optionally a surfactant and/or some about 6, about 8, about 10, about 12, about 14, about 16, about other additive, in the herbicidal compositions of the invention 18 or about 20 grams (a.e.) per liter). Accordingly, the gly is sufficient to provide at least about 80%, more preferably at phosate concentration may range, for example, from about 2 least about 85%, still more preferably at least about 90%, and 15 to about 50 grams (a.e.) per liter, from about 4 to about 25, still more preferably at least about 95%, control, or more, from about 6 to about 15, or from about 8 to about 12 grams within about 50 days, preferably about 40 days, more prefer (a.e.) per liter. In some instances, such as wherein: ably about 30 days, still more preferably about 20 days, still (i) the weight ratio (a.e. to a.e.) of glyphosate to the pyridine more preferably about 15 days, still more preferably about 10 analog is at least 4:1 (e.g., at least about 5:1, 6:1, 7:1, 8:1, days, still more preferably about 5 days, and even still more 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 40:1, 60:1, preferably about 1 day, or less, after application of the com 80:1, or even 100:1), the concentration of glyphosate may position to a plant. be no greater than 16.2 grams (a.e.) per liter (e.g., no Additionally, the concentrations of these herbicides, and greater than about 16, about 15.5, about 15, about 14.5, optionally a Surfactant and/or some other additive (as about 14, about 13.5, about 13, about 12.5, about 12, about described elsewhere herein), in the herbicidal compositions 25 11.5, about 11, about 10.5, about 10, about 9.5, about 9, of the invention is sufficient to provide at least about 70% about 8.5, about 8, about 7.5, about 7, about 6.5, about 6, control of plant regrowth (as determined by means known in about 5.5, about 5, etc., the concentration thus ranging the art) for at least about 20, preferably at least about 30, more from, for example, about 5 to about 16, from about 7 to preferably at least about 40, still more preferably at least about 14, or from about 8 to about 12, grams (a.e.) per about 50, still more preferably at least about 60, still more 30 liter); exemplary combinations include a ratio of at least preferably at least about 70, still more preferably at least 4:1, about 8:1, or even about 10:1 with a glyphosate con about 80, or even still more preferably at least about 90, days centration of less than about 15 grams (a.e.) per liter, 12 after application of the composition to a plant. In a more grams (a.e.) per liter, 10 grams (a.e.) per liter, or even 8 preferred embodiment, the concentrations of these herbi grams (a.e.) per liter; and/or cides, and optionally a surfactant and/or some other additive, 35 (ii) the weight ratio (a.e. to a.e.) of glyphosate to pyridine in the herbicidal compositions of the invention is sufficient to analog is at least 6:1 (e.g., at least about 7:1, 8:1, 9:1, 10:1, provide at least about 80%, more preferably at least about 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 40:1, 60:1, 80:1, or even 85%, still more preferably at least about 90%, or still more 100:1), the concentration of glyphosate may be no greater preferably at least about 95% control, or more, for at least than 23.8 grams (a.e.) per liter (e.g., no greater than about about 20, more preferably at least about 30, still more pref 40 23.5, about 23, about 22.5, about 22, about 21.5, about 21, erably at least about 40, still more preferably at least about 50, about 20.5, about 20, about 19.5, about 19, about 18.5, still more preferably at least about 60, still more preferably at about 18, about 17.5, about 17, about 16.5, about 16, about least about 70, still more preferably at least about 80, or even 15.5, about 15, about 14.5, about 14, about 13.5, about 13, still more preferably at least about 90, days after application about 12.5, about 12, about 11.5, about 11, about 10.5, to the plant. 45 about 10, about 9.5, about 9, about 8.5, about 8, about 7.5, Accordingly, in some embodiments of the present inven about 7, about 6.5, about 6, about 5.5, about 5, etc., the tion (e.g., the concentrate herbicidal composition), the gly concentration thus ranging from, for example, about 5 to phosate concentration may be at least about 50 grams, pref about 22, from about 6 to about 20, or from about 8 to about erably at least about 75 grams, more preferably at least about 15, grams (a.e.) per liter); exemplary combinations include 100 grams, still more preferably at least about 125 grams, still 50 a ratio of at least 6:1, about 8:1, or even about 10:1 with a more preferably at least about 150 grams, still more prefer glyphosate concentration of less than about 20grams (a.e.) ably at least about 175 grams, still more preferably at least per liter, 15 grams (a.e.) per liter, 12 grams (a.e.) per liter, about 200 grams, still more preferably at least about 225 10 grams (a.e.) per liter, or even 8 grams (a.e.) per liter. grams, still more preferably at least about 250 grams, (acid With respect to the glyphosate concentration, it is to be equivalent) per liter, or more (e.g., at least about 300grams, at 55 noted that as the concentration of glyphosate increases, the least about 350 grams, at least about 400 grams, at least about concentration of one or more other ingredients in the present 450 grams, at least about 500 grams, at least 550 grams, at composition may be reduced to maintain the Solubility of one least 600 grams per liter, or more). The glyphosate concen or more of the ingredients therein (i.e., to ensure these ingre tration may therefore range from, for example, about 50 to dients remain in Solution). about 500 grams (a.e.) per liter, from about 100 to about 400 60 The concentration of the pyridine analog in the herbicidal grams per liter, from about 150 to about 300grams per liter, or composition of the present invention may also vary. For from about 175 to about 250 grams per liter. example, the concentration may preferably be sufficient to In an alternative embodiment, the concentration of glypho provide visual symptoms of herbicide treatment within about sate may be no greater than 165 grams per liter (e.g., no 5 days, preferably about 4 days, or more preferably about 3 greater than 160 grams per liter, 155 grams per liter, 150 65 days after application of the composition to the plant, and in grams per liter, 140 grams per liter, or even no greater than Some instances may be sufficient to provide Such symptoms about 130, about 120, about 110, about 100, about 75 grams within about 2 days, about 1 day or even less, after the appli US 8,586,504 B2 15 16 cation. However, in this regard it is to be noted that the ingly, this ratio ranges from, for example, about 7.8:1 to about concentration of the pyridine analog is also preferably con 20:1, from about 8:1 to about 15:1, from about 8.4:1 to about trolled, such that it is not Substantially antagonistic to the 14:1, or about 9:1 to about 12:1. herbicidal activity of the glyphosate, or glyphosate derivative, Additionally, in yet other alternative embodiments (e.g., within the composition. 5 concentrate or ready-to-use compositions), wherein for Accordingly, in some embodiments of the present inven example picloram is used, the ratio of glyphosate to pyridine tion (e.g., the concentrate herbicidal composition), the con analog (e.g., picloram) may be greater than about 1:1 and less centration of the pyridine analog may be, for example, at least than about 32:1 range for example from about 5:1 to about about 1, about 2, about 4, about 6, about 8, about 10, about 15, 30:1, from about 10:1 to about 25:1, from about 11:1 to about about 20, about 25, about 30, about 35, about 40, about 45, 10 20:1, from about 12:1 to about 18:1, or from about 14:1 to about 50, about 60, about 70, about 80, about 90, about 100 or about 16:1. more grams (a.e.) per liter. The concentration of the pyridine In view of the foregoing, and as further described else analog may therefore range, for example, from about 1 to where herein, it is to be noted that the concentration of gly about 99 or 100 grams (a.e.) per liter (e.g., about 1 to about 99 phosate, the concentration of the pyridine analog (e.g., triclo or 100, about 2 to about 80, about 4 to about 60, about 6 to 15 pyr, clopyralid, fluoroxypyr, dithiopyr, thiazopyr, picloram, about 40, or about 8 to about 20, grams (a.e.) per liter). etc., or a combination thereof), the weight ratio of glyphosate In these or other embodiments of the present invention, it is to the pyridine analog, and/or the various ranges associated to be noted that the concentration may alternatively be not therewith, may be other than herein described without depart greater than 99 grams (a.e.) per liter (e.g., not greater than ing from the scope of the present invention. about 95, about 90, about 85, about 80, about 75, about 70, It is to be further noted that the various concentrations of about 65, about 60, about 55, about 50, about 40, about 30, the pyridine analog provided herein, as well as the various about 20, about 10, about 5 or less grams (a.e.) per liter). ratios of glyphosate to the pyridine analog, are intended to Accordingly, the concentration of the pyridine analog may apply independently to each analog, that is, although not range from, for example, about 1 to less than 99 grams (a.e.) specifically recited, it is to be noted that each concentration, per liter (e.g., from about 2 to less than about 80, from about 25 concentration range, ratio, etc. noted herein is intended to 4 to less than about 60, from about 6 to less than about 40, or apply independently triclopyr, clopyralid, fluoroxypyr, dithi from about 8 to less than about 20, grams (a.e.) per liter). opyr, thiazopyr, picloram, etc., or a combination thereof. In still other embodiments (e.g., a ready-to-use composi tion), the concentration of the pyridine analog may be less II. SURFACTANTS than about 25, about 15 or even about 10 grams (a.e.) liter, the 30 concentration ranging for example from about 0.2 to about 10 Various surfactants may be effective in formulating the grams (a.e.) per liter, from about 0.4 to about 6, from about 0.6 herbicidal compositions or concentrates of the present inven to about 4, or from about 0.8 to about 2 grams (a.e.) per liter. tion, including for example the nonionic, cationic, anionic Additionally, or alternatively, the concentration of the pyri and amphoteric Surfactants as described below, as well as dine analog may be not greater than 3.9 grams (a.e.) per liter 35 mixtures thereof. (e.g., not greater than about 3.8, about 3.7, about 3.6, about Cationic Surfactants effective in Such glyphosate composi 3.5, about 3.4, about 3.3, about 3.2, about 3.1, about 3, about tions or formulations include, for example: 2.8, about 2.6, about 2.4, about 2.2, about 2, about 1.8, about (a) a secondary or tertiary amine having the formula: 1.6, about 1.4, about 1.2, about 1, about 0.8, about 0.6, about 0.4, about 0.2 grams (a.e.) per liter or less, the concentration 40 ranging for example from about 0.2 to about 3.5 grams (a.e.) (1) per liter, from about 0.4 to about 3, from about 0.6 to about 2.5, or from about 0.8 to about 2 grams (a.e.) per liter). With respect to the weight ratio (a.e. to a.e.) of glyphosate to the pyridine analog, generally speaking this is greater than 45 about 1:1 (i.e., glyphosate is in excess); that is, this ratio may be at least about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, wherein R' and Rare hydrocarbyl having from 1 to about 30 about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, carbonatoms, and R is hydrogen or hydrocarbyl having from about 2:1, about 2.2:1, about 2.4:1, about 2.6:1, about 2.8:1, 1 to about 30 carbon atoms. In this context, preferred R', R. about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 50 and Rhydrocarbyl groups are linear or branched alkyl, linear 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, or branched alkenyl, linear or branched alkynyl, aryl, or about 14:1, about 15:1, about 20:1, about 25:1, about 30:1, aralkyl groups. Preferably, R is a linear or branched alkyl or about 35:1, about 40:1, about 45:1, about 50:1 or more (e.g., linear or branched alkenyl group having from about 8 to about about 60:1, about 70:1, about 80:1, about 90:1 or even about 30 carbon atoms, and R and Rare independently hydrogen 100:1). Accordingly, this ratio may range from about 1:1 to 55 or a linear or branched alkyl or linear or branched alkenyl about 100:1, from about 2:1 to about 8.0:1, from about 4:1 to group having from 1 to about 6 carbon atoms. More prefer about 60:1, from about 6:1 to about 40:1, or from about 8:1 to ably, R' is a linear or branched alkyl group having from about about 20:1. 12 to about 22 carbonatoms, andR and Rare independently Alternatively, in some embodiments (e.g., a ready-to-use hydrogen, methyl, ethyl, or linear or branched hydroxyalkyl composition), this ratio may be at least 7.6:1, and preferably 60 groups having from 1 to about 6 carbon atoms. may be at least about 7.7:1, about 7.8:1, about 7.9:1, about In an alternative embodiment, the Surfactant may have the 8:1, about 8.2:1, about 8.4:1, about 8.6:1, about 8.8:1, about formula (1) wherein R' is hydrocarbyl or substituted hydro 9:1, about 9.2:1, about 9.4:1, about 9.6:1, about 9.8:1, about carbyl having from about 8 to about 30 carbon atoms, R is a 10:1 or more (e.g., about 11:1, about 12:1, about 13:1, about hydroxyalkyl, polyhydroxyalkyl or poly(hydroxyalkyl)alkyl 14:1, about 15:1, about 20:1, about 25:1, about 30:1, about 65 group, and R is hydrogen, hydroxyalkyl, polyhydroxyalkyl 35:1, about 40:1, about 45:1, about 50:1, about 60:1, about or poly(hydroxyalkyl)alkyl. In this context, preferred R' 70:1, about 80:1, about 90:1 or even about 100:1). Accord hydrocarbyl groups are linear or branched alkyl, linear or US 8,586,504 B2 17 18 branched alkenyl, linear or branched alkynyl, aryl, or aralkyl groups. In one embodiment, R' is a linear or branched alkyl, 2ary to 3 (3) linear or branched alkenyl, linear or branched alkynyl, aryl, or (R-O), R X aralkyl group having from about 8 to about 30 carbon atoms, R’ is a linear or branched hydroxyalkyl group having from 1 R-y-Rior to about 6 carbon atoms, and R is hydrogen or a linear or R4 branched hydroxyalkyl group having from 1 to about 6 car bonatoms. Preferably, R is a linear or branched alkyl, linear wherein R' is hydrocarbylor substituted hydrocarbyl having or branched alkenyl, linear or branched alkynyl, aryl, or from 1 to about 30 carbonatoms, R in each of thex (RO)and aralkyl group having from about 8 to about 22 carbon atoms, 10 y (RO) groups is independently C-C alkylene, R is hydro R’ is a linear or branched hydroxyalkyl group having from 1 gen, or a linear or branched alkyl group having from 1 to to about 4 carbon atoms, and R is hydrogen or a linear or about 4 carbon atoms, R is hydrogen or hydrocarbyl or branched hydroxyalkyl group having from 1 to about 4 car substituted hydrocarbyl having from 1 to about 30 carbon bonatoms. More preferably, R is a linear or branched alkyl, atoms, Xandy are independently an average number from 1 to linear or branched alkenyl, linear or branched alkynyl, aryl, or 15 about 40, and X- is an agriculturally acceptable anion. In aralkyl group having from about 8 to about 18 carbon atoms, this context, preferred R' and R hydrocarbyl groups are R’ is hydroxymethyl or hydroxyethyl, and R is hydrogen, linear or branched alkyl, linear or branched alkenyl, linear or hydroxymethyl or hydroxyethyl. branched alkynyl, aryl, or aralkyl groups. Preferably, R' and (b) a monoalkoxylated amine having the formula: R" are independently a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 25 carbon (2) atoms, R in each of the X (RO) and y (RO) groups is (RO), R independently C-C alkylene, R is hydrogen, methyl or ethyl, and the sum of Xandy is an average number from about R-N V 25 2 to about 30. More preferably, R' and Rare independently R4 a linear or branched alkyl group having from 1 to about 22 carbon atoms, R in each of the X (RO) and y (RO) groups wherein R' and Rare independently hydrocarbyl or substi is independently ethylene or propylene, R is hydrogen or tuted hydrocarbyl groups having from 1 to about 30 carbon methyl, and the Sum of X and y is an average number from atoms or RSR, R in each of the X (RO) groups is 30 about 2 to about 20. Even more preferably, R is a linear or independently C-C alkylene, R is hydrogen, or a linear or branched alkyl group having from about 8 to about 22 carbon branched alkyl group having from 1 to about 4 carbon atoms, atoms and R is a linear or branched alkyl group having from R is a linear or branched alkyl group having from about 6 to 1 to about 22 carbon atoms, R in each of the X (RO) and y about 30 carbon atoms, R is a hydrocarbyl or substituted (RO) groups is independently ethylene or propylene, R is hydrocarbyl group having from 4 to about 15 carbon atoms 35 hydrogen or methyl, and the Sum of X and y is an average and X is an average number from 1 to about 60. In this context, number from about 2 to about 20. Most preferably, R is a preferred R', R', and Rhydrocarbyl groups are linear or linear or branched alkyl group having from about 8 to about branched alkyl, linear or branched alkenyl, linear or branched 22 carbon atoms and R is a linear or branched alkyl group alkynyl, aryl, or aralkyl groups. In one embodiment, R' having from 1 to about 6 carbon atoms, R in each of the X includes from about 7 to about 30 carbon atoms, preferably 40 (RO) and y (RO) groups is independently ethylene or pro from about 8 to about 22 carbon atoms, and the remaining pylene, R is hydrogen or methyl, and the sum of Xandy is an groups are as described above. Preferably, R' and R are average number from about 2 to about 15, or R' and Rare independently a linear or branched alkyl or linear or branched independently a linear or branched alkyl group having from alkenyl group having from 1 to about 25 carbon atoms, R in about 8 to about 22 carbon atoms, R in each of the X (RO) each of the X (RO) groups is independently C-C alkylene, 45 and y (RO) groups is independently ethylene or propylene, R is hydrogen, methyl or ethyl, and X is an average number R is hydrogen or methyl, and the sum of Xandy is an average from 1 to about 40. More preferably, R and Rare indepen number from about 5 to about 15. Preferred dialkoxylated dently a linear or branched alkyl group having from 1 to about quaternary ammonium surfactants include EthoduadTMC12 22 carbon atoms, R in each of the X (RO) groups is inde (a PEG 2 coco methyl ammonium chloride from Akzo pendently ethylene or propylene, R is hydrogen or methyl, 50 Nobel), PEG 5 coco methyl ammonium chloride, PEG 5 and x is an average number from 1 to about 30. Even more tallow methyl ammonium chloride, PEG 5 ditallow ammo preferably, R is a linear or branched alkyl group having from nium bromide, and PEG 10 ditallow ammonium bromide. about 8 to about 22 carbon atoms and R is a linear or (d) a monoalkoxylated quaternary ammonium salt having branched alkyl group having from 1 to about 22 carbonatoms, the formula: R’ in each of thex (RO) groups is independently ethylene or 55 propylene, R is hydrogen or methyl, and X is an average number from about 1 to about 10. Most preferably, R' is a (4) linear or branched alkyl group having from about 16 to about i X 22 carbon atoms and R is methyl, R in each of the X (RO) groups is ethylene, R is hydrogen, and X is an average num 60 ber from about 1 to about 5, or R' is a linear or branched alkyl R4 group having from about 8 to about 15 carbon atoms and R' is methyl, R in each of the X (RO) groups is ethylene, R is wherein R' and Rare independently hydrogen or hydrocar hydrogen, and X is an average number from about 5 to about byl or substituted hydrocarbyl having from 1 to about 30 10. 65 carbon atoms, R is hydrocarbyl or substituted hydrocarbyl (c) a dialkoxylated quaternary ammonium salt having the having from 1 to about 30 carbon atoms, R in each of the X formula: (RO) groups is independently C-C alkylene, R is hydro US 8,586,504 B2 19 20 gen, or a linear or branched alkyl group having from 1 to from about 8 to about 14 carbonatoms, and R. RandR are about 30 carbon atoms, X is an average number from 1 to methyl. Preferred commercially available quaternary ammo about 60, and X- is an agriculturally acceptable anion. In nium surfactants include ArquadTMC-50 (a dodecyl trimethyl this context, preferred R', R', and Rhydrocarbyl groups are ammonium chloride from AkzoNobel) and ArquadTMT-50 (a linear or branched alkyl, linear or branched alkenyl, linear or tallow trimethyl ammonium chloride from Akzo Nobel). branched alkynyl, aryl, or aralkyl groups. Preferably, R', R' (f) an ether amine having the formula: and Rare independently a linear or branched alkyl or linear or branched alkenyl group having from 1 to about 25 carbon atoms, R in each of the X (RO) groups is independently (6) C-C alkylene, R is hydrogen, methyl or ethyl, and X is an 10 average number from 1 to about 40. More preferably, R. R. and Rare independently a linear or branched alkyl group having from 1 to about 22 carbon atoms, R in each of the X (RO) groups is independently ethylene or propylene, R is 15 wherein R' is hydrocarbyl or substituted hydrocarbyl having hydrogen or methyl, and X is an average number from 1 to from 1 to about 30 carbon atoms; R is hydrocarbylene or about 30. Even more preferably, R' is a linear or branched substituted hydrocarbylene having from 2 to about 30 carbon alkyl group having from about 8 to about 22 carbonatoms, R atoms; RandR are independently hydrogen, hydrocarbylor in each of the X (RO) groups is independently ethylene or substituted hydrocarbyl having from 1 to about 30 carbon propylene, R is hydrogen or methyl, Rand Rare indepen atoms, or —(RO),R, R in each of the x(R-O) groups is dently a linear or branched alkyl group having from 1 to about independently C-C alkylene, R is hydrogen, or a linear or 22 carbon atoms, and X is an average number from 1 to about branched alkyl group having from 1 to about 4 carbon atoms, 30. Even more preferably, R' is a linear or branched alkyl and X is an average number from 1 to about 50. In this context, group having from about 8 to about 22 carbon atoms, R in preferred R', R. R. and Rhydrocarbyl (hydrocarbylene) each of the X (RO) groups is independently ethylene or 25 groups are linear or branched alkyl (alkylene), linear or propylene, R is hydrogen or methyl, Rand Rare indepen branched alkenyl (alkenylene), linear or branched alkynyl dently a linear or branched alkyl group having from 1 to about (alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. 6 carbon atoms, and X is an average number from about 5 to about 25. Most preferably, R is a linear or branched alkyl Preferably, R is a linear or branched alkyl, linear or branched group having from about 16 to about 22 carbon atoms, R in alkenyl, linear or branched alkynyl, aryl, or aralkyl group each of the X (RO) groups is independently ethylene or 30 having from 8 to about 25 carbon atoms, R is a linear or propylene, R is hydrogen or methyl, RandR are indepen branched alkylene or alkenylene group having from 2 to dently a linear or branched alkyl group having from 1 to about about 30 carbon atoms, RandR are independently hydro 3 carbon atoms, and X is an average number from about 5 to gen, a linear or branched alkyl, linear or branched alkenyl, about 25. Preferred monoalkoxylated quaternary ammonium linear or branched alkynyl, aryl, or aralkyl group having from 35 1 to about 30 carbonatoms, or—(RO),R, R in each of the surfactants include PEG 7 Cs dimethyl ammonium chloride X (RO) groups is independently C-C alkylene, R is hydro and PEG 22 Cs dimethyl ammonium chloride. gen, methyl or ethyl, and X is an average number from 1 to (e)a quaternary ammonium salt having the formula: about 30. More preferably, R is a linear or branched alkyl or alkenyl group having from 8 to about 22 carbon atoms, R is 40 a linear or branched alkylene or alkenylene group having (5) from 2 to about 6 carbon atoms, Rand Rare independently hydrogen, a linear or branched alkyl or alkenyl group having from 1 to about 6 carbonatoms, or—(RO),R, R in each of the X (RO) groups is independently ethylene or propylene, 45 R is hydrogen or methyl, and X is an average number from 1 to about 15. Most preferably, R is a linear or branched alkyl wherein R', RandR are independently hydrogen or hydro or alkenyl group having from 8 to about 18 carbonatoms, R carbyl or substituted hydrocarbyl having from 1 to about 30 is ethylene or propylene, RandR are independently hydro carbon atoms, R is hydrocarbyl or substituted hydrocarbyl gen, methyl, or—(RO),R, R in each of thex (RO) groups having from 1 to about 30 carbon atoms, and X- is an 50 is independently ethylene or propylene, R is hydrogen, and X agriculturally acceptable anion. In this context, preferred R', is an average number from 1 to about 5. R. R. and R hydrocarbyl groups are linear or branched (g) a diamine having the formula: alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl groups. Preferably, R is a linear or branched alkyl or linear or branched alkenyl group having from about 8 55 to about 30 carbon atoms, and R, R and R are indepen (7) dently a linear or branched alkyl or linear or branched alkenyl R-X-R-i-ro-R-N-R group having from 1 to about 30 carbon atoms. More prefer ably, R is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 22 carbon atoms, 60 wherein R', R, R and R are independently hydrogen, and R. RandR are independently a linear or branched alkyl hydrocarbyl or substituted hydrocarbyl having from 1 to or linear or branched alkenyl group having from 1 to about 6 about 30 carbon atoms, or—(RO),R'; R and Rare inde carbon atoms. Even more preferably, R is a linear or pendently hydrocarbylene or substituted hydrocarbylene branched alkyl group having from about 8 to about 16 carbon having from 2 to about 30 carbon atoms, R in each of the X atoms, and R, R and R are independently a linear or 65 (RO) and y (RO) groups is independently C-C alkylene, branched alkyl group having from 1 to about 6 carbon atoms. R’ is hydrogen, or a linear or branched alkyl group having Most preferably, R is a linear or branched alkyl group having from 1 to about 30 carbonatoms, X is an average number from US 8,586,504 B2 21 22 1 to about 30, X is —O , N(R) , —C(O) , —C(O) branched alkyl group having from about 1 to about 22 carbon O –OC(O) - N(R)C(O) = C(O)N(R) - S -, atoms, R is a linear or branched alkylene group having from —SO—, or—SO , y is 0 or an average number from 1 to about 2 to about 6 carbon atoms, R. R. and R are each about 30, n and Zare independently 0 or 1, and R is hydrogen independently hydrogen, X is —C(O)—or —SO , nandy or hydrocarbyl or substituted hydrocarbyl. In this context, are 0 and Z is 1. Preferred diamines include Gemini 14-2-14, preferred R', R. R. R. Rand Rhydrocarbyl (hydrocar Gemini 14-3-14, Gemini 10-2-10, Gemini 10-3-10, Gemini bylene) groups are linear or branched alkyl (alkylene), linear 10-4-10, and Gemini 16-2-16 (Co. C or C ethylene, pro or branched alkenyl (alkenylene), linear or branched alkynyl pylene or butylene N-methyl diamines from Monsanto), (alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. Ethoduomeens TM, and JeffamineTMEDR-148. Preferably, R' and Rare independently a linear or branched 10 alkyl or linear or branched alkenyl group having from about 1 (h) an amine oxide having the formula: to about 22 carbon atoms, R and Rare independently linear or branched alkylene groups having from about 2 to about 25 (8) carbonatoms, Rand Rare each independently hydrogen or O a linear or branched alkyl group having from 1 to about 6 15 carbon atoms and n, y and Z are 0; or R', R, R and Rare R-N-R independently hydrogen or a linear or branched alkyl or alk R2 enyl group having from about 1 to about 6 carbon atoms, R is a linear or branched alkylene or alkenylene group having from about 8 to about 25 carbon atoms, and n, y and Z are 0; wherein R, R and Rare independently hydrogen, hydro or R. R. Rand Rare independently hydrogen or a linear or carbyl or substituted hydrocarbyl, -(RO),R, or —R branched alkyl or alkenyl group having from about 1 to about (OR), OR: R in each of the X (RO) groups is indepen 6 carbon atoms, R is a linear or branched alkylene or alk dently C-C alkylene, R is hydrogen, or a linear or branched enylene group having from about 1 to about 6 carbon atoms, alkyl group having from 1 to about 30 carbon atoms, R is R’ in each of they (RO) groups is independently C-C, 25 hydrocarbylene or substituted hydrocarbylene having from 2 alkylene, y is an average number from 1 to about 20 and n and to about 6 carbon atoms, X in each of the X (RO) groups is Zare 0; or R' and Rare independently a linear or branched independently an average number from 1 to about 50, and the alkyl or linear or branched alkenyl group having from about 8 total number of carbon atoms in R', RandR is at least 8. In to about 22 carbonatoms, R is a linear or branched alkylene this context, preferred R', R. R. and Rhydrocarbyl (hydro group having from about 2 to about 25 carbon atoms; and R' 30 carbylene) groups are linear or branched alkyl (alkylene), and Rare each independently hydrogen, a linear or branched linear or branched alkenyl (alkenylene), linear or branched alkyl or alkenyl group having from 1 to about 6 carbon atoms, alkynyl (alkynylene), aryl (arylene), or aralkyl (aralkylene) or —(RO), R. R. in each of the X (RO) groups is indepen groups. Preferably, R' and Rare independently hydrogen, a dently C-C alkylene, R is hydrogen, or a linear or branched linear or branched alkyl or linear or branched alkenyl group alkyl group having from 1 to about 4 carbon atoms, X is an 35 having from 1 to about 30 carbon atoms, or —(RO), R. R. average number from 1 to about 30, and n, y and Zare 0; or R' is a linear or branched alkyl or linear or branched alkenyl is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R' in group having from about 1 to about 22 carbon atoms, R is a each of the X (RO) groups is independently C-C alkylene; linear or branched alkylene group having from about 2 to R is hydrogen, methyl or ethyl, and X is an average number about 25 carbonatoms, R. Rand Rare each independently 40 from 1 to about 30. More preferably, R' and Rare indepen hydrogen or a linear or branched alkyl group having from 1 to dently hydrogen, or a linear or branched alkyl group having about 6 carbonatoms, X is —C(O)—or —SO. , nandy are from 1 to about 6 carbonatoms, and R is a linear or branched 0 and Z is 1. More preferably, R' and Rare independently a alkyl group having from about 8 to about 22 carbon atoms; or linear or branched alkyl or linear or branched alkenyl group R" and R are independently —(RO), R, R is a linear or having from about 4 to about 18 carbon atoms, R is a linear 45 branched alkyl group having from about 8 to about 22 carbon or branched alkylene group having from about 2 to about 6 atoms, R' in each of the X (RO) groups is ethylene or pro carbonatoms, Rand Rare each independently hydrogen or pylene, R is hydrogen or methyl, and X is an average number a linear or branched alkyl group having from 1 to about 6 from 1 to about 10. Most preferably, R' and Rare indepen carbon atoms, and n, y and Z are 0; or R', R. RandR are dently methyl, and R is a linear or branched alkyl group independently hydrogen or a linear or branched alkyl group 50 having from about 8 to about 18 carbon atoms; or R' and R' having from about 1 to about 6 carbonatoms, R is a linear or are independently —(RO),R, R is a linear or branched branched alkylene group having from about 8 to about 25 alkyl group having from about 8 to about 18 carbonatoms, R carbon atoms, and y is 0; or R', R, R and Rare indepen in each of the X (RO) groups is ethylene or propylene, R is dently hydrogen or a linear or branched alkyl group having hydrogen, and X is an average number from 1 to about 5. from about 1 to about 6 carbon atoms, R is a linear or 55 Commercially available amine oxide Surfactants include branched alkylene group having from about 1 to about 6 Chemoxide L70. carbon atoms, R in each of they (RO) groups is indepen (i) a dialkoxylated amine having the formula: dently ethylene or propylene, y is an average number from 1 to about 10 and n and Z is 0; or R' and Rare independently a linear or branched alkyl group having from about 8 to about 60 (9) 22 carbon atoms, R is a linear or branched alkylene group (RO), R having from about 2 to about 6 carbon atoms, and RandR R-N are each independently hydrogen, a linear or branched alkyl Yeo R3 group having from 1 to about 6 carbonatoms, or—(RO),R". ( y R’ in each of thex (RO) groups is independently ethylene or 65 propylene, R is hydrogen or methyl, X is an average number wherein R' is a hydrocarbyl or substituted hydrocarbyl hav from 1 to about 15, and n, y and Z are 0; or R' is a linear or ing from about 6 to about 30 carbon atoms, or—RSR, R' US 8,586,504 B2 23 24 and R in each of the X (RO) and they (RO) groups is independently C-C alkylene, R is hydrogen, or a linear or (11) branched alkyl group having from 1 to about 4 carbon atoms, R is a linear or branched alkyl group having from about 4 to W about 15 carbon atoms, and X and y are independently an average number from 1 to about 40. In this context, preferred R" hydrocarbyl groups are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl wherein R' is hydrogen or hydrocarbylor substituted hydro groups. Preferably, R is a linear or branched alkynyl, aryl, or carbyl having from 1 to about 30 carbonatoms; R in each of aralkyl group having from about 8 to about 30 carbon atoms, 10 the X (RO) and y (RO) groups is independently C-C, R’ in each of the X (RO) and they (RO) groups is indepen alkylene; R is hydrocarbylene or substituted hydrocarbylene dently C-C alkylene, R is hydrogen, methyl or ethyl, and X having from 2 to about 30 carbon atoms; R and Rare each and y are independently an average number from 1 to about independently hydrogen, hydrocarbyl or substituted hydro carbyl having from 1 to about 30 carbon atoms, —(R), 20. More preferably, R is a linear or branched alkynyl, aryl, 15 or aralkyl group having from about 8 to about 25 carbon (RO),R', or R and R, together with the nitrogen atom to atoms, R in each of the X (RO) and they (RO) groups is which they are attached, forma cyclic or heterocyclic ring; R' independently ethylene or propylene, R is hydrogen or is hydrocarbylene or substituted hydrocarbylene having from 1 to about 30 carbon atoms; R is hydrogen or a linear or methyl, and X and y are independently an average number branched alkyl group having 1 to about 4 carbonatoms, n is 0 from 1 to about 30. Even more preferably, R is a linear or or 1, X and y are independently an average number from 1 to branched alkynyl, aryl, or aralkyl group having from about 8 about 60. In this context, preferred R', R. R. R. and R' to about 22, or about 12 to about 22, carbonatoms, R in each hydrocarbyl (hydrocarbylene) groups are linear or branched of the X (RO) and they (RO) groups is independently alkyl (alkylene), linear or branched alkenyl (alkenylene), lin ethylene or propylene, R is hydrogen or methyl, and Xandy ear or branched alkynyl (alkynylene), aryl (arylene), or are independently an average number from 1 to about 5. Some 25 aralkyl (aralkylene) groups. Preferably, R is a linear or commercially available dialkoxylated amines include, for branched alkyl or linear or branched alkenyl group having example, TrymeenTM 6617 (from Cognis) and EthomeenTM from about 8 to about 25 carbon atoms, R in each of the X C/12, C/15, C/20, C/25, T/12, T/15, T/20 and T/25 (from (RO) groups is independently C-C alkylene, R is a linear Akzo Nobel). or branched alkylene group having from 2 to about 20 carbon and () an aminated alkoxylated alcohol having the for 30 atoms, Rand Rare each independently hydrogen or a linear mula: or branched alkyl group having from 1 to about 6 carbon atoms, and X is an average number from 1 to about 30. More preferably, R is a linear or branched alkyl group having from (10) about 12 to about 22 carbon atoms, R in each of the X (RO) R5 R7 35 groups is independently ethylene or propylene, R is a linear W or branched alkylene group having from 2 to about 6 carbon R-X-(R)-(RO), -R-(NR), -N atoms, R and Rare each independently hydrogen, methyl, R8 or tris(hydroxymethyl)methyl, and X is an average number from about 2 to about 30. Even more preferably, R is a linear wherein R. R. R. and Rare each independently hydrogen, 40 or branched alkyl group having from about 12 to about 18 carbon atoms, R in each of the X (RO) groups is indepen hydrocarbyl or substituted hydrocarbyl having from 1 to dently ethylene or propylene, R is ethylene or propylene, R' about 30 carbon atoms, or —(R'),(RO),R': X is —O , and Rare each independently hydrogen, methyl or tris(hy –OC(O) , C(O)O-, - N(R')C(O) , C(O)N droxymethyl)methyl, and X is an average number from about (R') , S: , SO , -SO, or N(R) : R in each 45 4 to about 20. Most preferably, R' is a linear or branched alkyl of the n (RO) groups and the V (RO) groups is indepen group having from about 12 to about 18 carbon atoms, R in dently C-C alkylene; R' is hydrogen, or a linear or each of the X (RO) groups is independently ethylene or branched alkyl group having from 1 to about 30 carbon propylene, R is ethylene, R and Rare methyl, and x is an atoms; n is an average number from 1 to about 60; V is an average number from about 4 to about 20. Preferred average number from 1 to about 50; R and R'' are each 50 monoalkoxylated amines include PEG 13 or 18 Cas ether independently hydrocarbylene or substituted hydrocarbylene propylamines and PEG 7, 10, 15 or 20 Cls ether propy having from 1 to about 6 carbon atoms; R is hydrocarbylene lamines (from Tomah) and PEG 13 or 18 Cas ether dim or substituted hydrocarbylene having from 2 to about 6 car ethyl propylamines and PEG 10, 15 or 20 or 25 Cls ether bon atoms; R' is hydrogen or hydrocarbyl or substituted dimethyl propylamines (from Tomah) and SurfonicTMAGM hydrocarbyl having from 1 to about 30 carbon atoms; m and 55 s are each independently 0 or 1; R is hydrocarbylene or 550 from Huntsman. substituted hydrocarbylene having from 2 to about 30 carbon Quaternary ammonium, Sulfonium and Sulfoxonium salts atoms, –C(=NR') , —C(S)-, or—C(O)—; q is an inte are also effective cationic Surfactants in forming glyphosate ger from 0 to 5; and R is hydrogen or hydrocarbyl or substi concentrates and have the chemical structures: tuted hydrocarbyl having from 1 to about 30 carbonatoms. In 60 this context, preferred R', R. R. R. R. R. R. R. R'' and R" hydrocarbyl (hydrocarbylene) groups are linear or (12) branched alkyl (alkylene), linear or branched alkenyl (alk enylene), linear or branched alkynyl (alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. 65 A Subclass of Such cationic Surfactants includes R9 O monoalkoxylated amines having the formula: US 8,586,504 B2 25 26 -continued alkynyl (alkynylene), aryl (arylene), or aralkyl (aralkylene) (13) groups. In one embodiment of formula (DA), R is hydrocar bylene having from about 2 to about 6 carbon atoms, and the R10 R5 R7 remaining groups are as defined above. Preferred nonionic Surfactants for Such glyphosate concen A R--R-Ro-R-N-- A trates include alkoxylated alcohols having the formula: RI R9 O RO (R’O).R (18) (14) wherein R' is hydrocarbylor substituted hydrocarbyl having R10 R5 R7 from 1 to about 30 carbon atoms, R in each of the X (RO) 10 groups is independently C-C alkylene, R is hydrogen, or a A R-s-le-Ro-R-N-- A linear or branched alkyl group having from 1 to about 4 R9 O carbonatoms, and X is an average number from 1 to about 60. (15) In this context, preferred R' hydrocarbyl groups are linear or branched alkyl, linear or branched alkenyl, linear or branched O R5 R7 15 alkynyl, aryl, or aralkyl groups. Preferably, R is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms, R in each of the X (RO) groups is independently C-C alkylene, R is hydro gen, methyl or ethyl, and X is an average number from about 5 to about 50. More preferably, R is a linear or branched alkyl wherein R', R,R,R,R'' and R'' are independently hydro group having from about 8 to about 25 carbon atoms, R in gen, hydrocarbyl or substituted hydrocarbyl having from 1 to each of the X (RO) groups is independently ethylene or about 30 carbon atoms, or -(R') (RO),R'': X is -O-, propylene, R is hydrogen or methyl, and X is an average OC(O) , N(R')C(O) C(O)N(R') C(O) number from about 8 to about 40. Even more preferably, R is O—, or S : R in each of then (RO) groups and V (RO) a linear or branched alkyl group having from about 12 to groups is independently C-C alkylene; R' is hydrogen, or 25 about 22 carbon atoms, R in each of the X (RO) groups is a linear or branched alkyl group having from 1 to about 30 independently ethylene or propylene, R is hydrogen or carbonatoms; n is an average number from 1 to about 60; V is methyl, and X is an average number from about 8 to about 30. an average number from 1 to about 50: R and R' are each Preferred commercially available alkoxylated alcohols independently hydrocarbylene or substituted hydrocarbylene include ProcolTMLA-15 (from Protameen), BriTM35, BriTM having from 1 to about 6 carbon atoms; m and S are each 30 76, BriTM 78, BriTM 97 and BriTM 98 (from Sigma Chemical independently 0 or 1; R is hydrocarbylene or substituted Co.), NeodolTM25-12 (from Shell), HexotolTMCA-10, Hexo hydrocarbylene having from 2 to about 6 carbonatoms; R is tolTM CA-20, HexotolTM CS-9, HexotolTM CS-15, HexotolTM hydrocarbylene or substituted hydrocarbylene having from 2 CS-20, HexotolTM CS-25, HexotolTM CS-30, and PlurafacTM to about 30 carbon atoms, —C(=NR') , —C(S) , or A38 (from BASF), ST-8303 (from Cognis), and ArosurftM 66 —C(O) ; R'' is hydrogen or hydrocarbyl or substituted 35 E20 (from Witco/Crompton). hydrocarbyl having from 1 to about 30 carbon atoms, q is an Other nonionic Surfactants for use in Such glyphosate com integer from 0 to 5; R is hydrogen or hydrocarbyl or substi positions or formulations include alkoxylated dialkylphenols tuted hydrocarbyl having from 1 to about 30 carbon atoms: having the formula: and each A is an agriculturally acceptable anion. In this context, preferred R', R. R. R. R. R. R. R. R. R'', 40 (19) R', and R' hydrocarbyl (hydrocarbylene) groups are linear RI or branched alkyl (alkylene), linear or branched alkenyl (alk enylene), linear or branched alkynyl (alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. Other cationic Surfactants effective in any glyphosate com 45 position or formulation are diamines or diammonium salts R4 having the formulas: (OR2), R wherein R' and Rare independently hydrogen, or a linear or 50 branched alkyl group having from 1 to about 30 carbon atoms R6 Rs O and at least one of R' and R is an alkyl group, R in each of (17) the X (RO) groups is independently C-C alkylene, R is Rs R hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbonatoms, and X is an average number from 1 to about 60. Preferably, R' and R are independently linear or 55 branched alkyl groups having from 8 to about 30 carbon R6 Rs atoms, R in each of the X (RO) groups is independently wherein R. R. R. R. R7 and Rare independently hydro C-C alkylene, R is hydrogen, methyl or ethyl, and X is an gen or hydrocarbyl or substituted hydrocarbyl having from 1 average number from about 5 to about 50. More preferably, to about 30 carbon atoms, R in each of the m (RO) and in R" and Rare independently linear or branched alkyl groups (RO) groups and Rare independently C-C alkylene, R is 60 having from about 8 to about 22 carbon atoms, R in each of hydrocarbylene or substituted hydrocarbylene having from the X (RO) groups is independently ethylene or propylene, about 2 to about 6 carbon atoms or (RO).R. , m and in R is hydrogen or methyl, and X is an average number from are individually an average number from 0 to about 50, and p about 8 to about 40. Even more preferably, R' and R are is an average number from 0 to about 60. In this context, independently linear or branched alkyl groups having from preferred R', R. R. R. R. R7 and Rhydrocarbyl (hydro 65 about 8 to about 16 carbon atoms, R in each of the X (RO) carbylene) groups are linear or branched alkyl (alkylene), groups is independently ethylene or propylene, R is hydro linear or branched alkenyl (alkenylene), linear or branched gen or methyl, and X is an average number from about 10 to US 8,586,504 B2 27 28 about 30. Preferred commercially available alkoxylated composition, described herein, the weight ratio of glyphosate dialkylphenols include ethoxylated dinonyl phenols such as (a.e. basis) to surfactant may range from about 1:10 to 10:1 or SurfonicTM DNP 100, SurfonicTM DNP 140, and SurfonicTM more (e.g., from about 1:8 to 8:1, from about 1:6 to about 6:1, DNP 240 (from Huntsman). from about 1:4 to about 4:1, from about 1:3 to about 3:1, or Preferred anionic surfactants effective in forming glypho from about 1:2 to about 2:1). Alternatively, this ratio may sate compositions or formulations, in at least Some embodi range from about 1:1 to about 10:1 (e.g., from about 1:1 to ments, may include Saturated carboxylic acids such as about 10:1, from about 2:1 to about 8:1, or from about 3:1 to butyric, caproic, caprylic, capric, lauric, palmitic, myristic or about 6:1), from about 1:1 to about 15:1, from about 1:1 to Stearic acid, and unsaturated carboxylic acids such as palmi about 20:1, or more. Accordingly, exemplary ratios include toleic, oleic, linoleic or linolenic acid. Preferred carboxylic 10 about 1:10, about 1:9.5, about 1:9, about 1:8.5, about 1:8, acids, in at least some embodiments, may include palmitic, about 1:7.5, about 1:7, about 1:6.5, about 1:6, about 1:5.5, oleic or Stearic acid. Other preferred anionic Surfactants, in at about 1:5, about 1:4.5, about 1:4, about 1:3.5, about 1:3, about least some embodiments, may include alkyl Sulfates Such as 12.5, about 1:2, about 1:1.5, about 1:1, about 1.5:1, about 2:1, Sodium lauryl Sulfate, and alkyl alkoxylated phosphates hav about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1, ing the formulae: 15 about 5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, about 7.5:1, about 8:1, about 8.5:1, about 9:1, about 9.5:1, about 10:1, about 11:1, about 12:1, about 13:1, about 14:1, about (20) 15:1, about 16:1, about 17:1, about 18:1, about 19:1, about 20:1 or more. R-O-(RO)1 O H. Alternatively, in these or other embodiments (e.g., a ready to-use composition), the weight ratio of glyphosate (a.e. basis) to surfactant may range from about 10:1 to about 1:5 wherein R' and R are independently a linear or branched (e.g., from about 8:1 to about 1:4, from about 6:1 to about 1:3, alkyl, linear or branched alkenyl, linear or branched alkynyl, from about 4:1 to about 1:2, or from about 2:1 to about 1:1). aryl, or aralkyl group having from about 4 to about 30 carbon 25 Additionally, in these or other embodiments, the surfactant atoms; R in each of the m (RO) and the n (RO) groups is concentration may be at least about 1 gram per liter (e.g., at independently C-C alkylene; and mand nare independently least about 5, 10, 20, 30, 40, 50, 60, 70, 80,90, 100, 125, 150, from 1 to about 30; or 200, 250, 300, 350, 400, 450, 500 grams per liter or more), ranging for example from about 1 to about 500grams per liter, 30 from about 5 to about 250 grams per liter, 10 to about 100 (21) grams per liter, from about 20 to about 80 grams per liter, or R-O-(RO), P 29 H from about 40 to about 60 grams per liter. Alternatively, the Hi O1 No Surfactant concentration may range from about 1 to 283 grams per liter (e.g., ranging for example from about 1 to wherein R' is a linear or branched alkyl, linear or branched 35 about 275 grams per liter, from about 5 to about 250 grams per alkenyl, linear or branched alkynyl, aryl, or aralkyl group liter, from about 10 to about 100grams per liter, from about 20 having from about 8 to about 30 carbon atoms; R in each of to about 80grams per liter, or from about 40 to about 60 grams the m (RO) groups is independently C-C alkylene; and m per liter). is from 1 to about 30. Representative alkyl alkoxylated phos In some embodiments (e.g., a ready-to-use composition), phates include oleth-10 phosphate, oleth-20 phosphate and 40 the Surfactant concentration may not be greater than 3.9 oleth-25 phosphate. Other representative alkyl alkoxylated grams per liter (e.g., not greater than 3.8, 3.6, 3.4, 3.2, 3, 2.8, phosphates include those wherein, in (21), R has about 10 to 2.6, 2.4, 2.2, 2, 1.8, 1.6, 1.4, 1.2, 1 or less), when the weight about 15 carbonatoms, R is ethylene or propylene, and mis ratio (a.e. to a.e.) of glyphosate to pyridine analog (triclopyr, from about 1 to about 10, from about 2 to about 8, or about 4 for example) is at least 3:1. In these or other embodiments, the to about 6. 45 Surfactant concentration may not be greater than 6.6 grams Other exemplary Surfactants that may be used in accor per liter (e.g., not greater than 6.4., 6.2, 6, 5.8, 5.6, 5.4, 5.2, 5, 4.8, 4.6, 4.4, 4.2, 4, 3.8, etc.), when the weight ratio (a.e. to dance with the present invention include the following spe a.e.) of glyphosate to pyridine analog (triclopyr, for example) C1S is at least 5:1. In these or still other embodiments, the surfac 50 tant concentration may not be greater than 9.3 grams per liter (e.g., not greater than 9.2, 9.8.8, 8.6, 8.4, 8.2, 8, 7.8, 7.6, 7.4, 7.2, 7, 6.8, 6.6, 6.4, etc.), when the weight ratio (a.e. to a.e.) of glyphosate to pyridine analog (triclopyr, for example) is at least 7:1. 55 III. PROPERTIES CH CH and (23) Among the various properties of the compositions of the C C present invention is to be noted that these compositions typi CH3 CH3 60 cally have a cloud point of at least about 50°C., or even about 60° C. Additionally, the aqueous concentrate and/or the ready-to-use composition of the present invention typically has a composition Such that triclopyr (or more generally the CH CH pyridine analog) will not crystallize or precipitate when the 65 bulk solution freezes or solidifies, and then thaws; stated In at least Some embodiments of one or more of the aque another way, the herbicide compositions or formulations of ous or dry concentrates, or alternatively the ready-to-use the present invention have a composition wherein the pyri US 8,586,504 B2 29 30 dine analog, such as triclopyr, will not precipitate upon being groups is independently C-C alkylene; R is hydrocarby cooled to a temperature of about 0°C., or even about -10°C. lene or substituted hydrocarbylene having from 2 to about 6 carbon atoms; and A- is an agriculturally acceptable anion. IV. OPTIONAL ADDITIVES Optionally, one or more of the compositions of the present invention may further comprise one or more additional pes As further discussed herein, other additives, adjuvants, or ticides, such as for example, water-soluble herbicidal active ingredients may be introduced into the compositions or for ingredients, including without restriction water-soluble mulations of the present invention to improve certain proper forms of acifluorfen, asulam, benazolin, bentazon, bialaphos, ties thereof (e.g., Solubility of the pyridine analog). Although bispyribac, bromacil, bromoxynil, carfentraZone, chloram the compositions or formulations of the present invention 10 ben, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, generally show good overall stability and Viscosity properties difenZoquat, diduat, endothall, fenac, fenoxaprop, flamprop, without the addition of any further additives, the addition of a fluazifop, fluoroglycofen, fomesafen, fosamine, glufosinate, solubilizer (also commonly referred to as a cloud point haloxyflop, imazameth, imazamethabenz, imaZamox, imaza enhancer or stabilizer) may significantly improve the proper pic, imazapyr, imaZaquin, imazethapyr, ioxynil, MCPA, 15 MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic ties of the compositions or formulations of the present inven acid, paraquat, Sulfamic acid, 2.3.6-TBA, TCA, acetochlor, tion. Suitable solubilizers for use with the novel compositions aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atra or formulations of the present invention include, for example, Zine, azafenidin, azimsulfuron, benfluralin, benfuresate, ben cocoamine (Armeen C), dimethylcocoamine (Arquad sulfuron-methyl, bensulide, benzofenap, bifenox, bro DMCD), cocoammonium chloride (Arquad C), PEG 2 mobutide, bromofenoxim, butachlor, butamifos, butralin, cocoamine (Ethomeen C12), a cocodiamine 3EO butroxydim, butylate, cafenstrole, carbetamide, carfentra (Ethoduomeen CD/13), PEG 5tallowamine (Ethomeen T15), Zone-ethyl, chlomethoxyfen, chlorbromuron, chloridazon, and PEG 5 cocoamine (Ethomeen C15), all of which are chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlor manufactured by Akzo Nobel (California). propham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, Additionally, it has been found that the addition of a C to 25 cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl. C alkyl or aryl amine compound, or the corresponding clomaZone, clomeprop, cloranSulam-methyl, cyanazine, quaternary ammonium compound, greatly enhances the com cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, patibility of certain glyphosate salts (e.g., potassium or iso daimuron, desmedipham, desmetryn, dichlobenil, diclofop propylamine) with surfactants that otherwise exhibit low or marginal compatibility at a given glyphosate loading. Suit methyl, diflufenican, dimefuron, dimepiperate, dimeth 30 achlor, dimethametryn, dimethenamid, dinitramine, dinot able alkyl or aryl amine compounds may also contain 0 to erb, diphenamid, diuron, EPTC, esprocarb, ethal fluralin, about 5 EO groups. Preferred alkylamine compounds include ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, eto C to C2 alkylamines having 0 to 2 EO groups. Similarly, benzanid, fenoxaprop-ethyl, fenuron, flamprop-methyl, fla etheramine compounds having 4 to 12 carbons and 0 to about Zasulfuron, fluazifop-butyl, fluchloralin, flumetsulam, flumi 5 EO groups, as well as the corresponding quaternary ammo 35 clorac-pentyl, flumioxazin, fluometuron, fluorochloridone, nium compounds, also enhance the compatibility of Such fluoroglycofen-ethyl, flupoxam, flurenol, fluridone, flurta compositions or formulations. In one embodiment, the com pounds which enhance the compatibility of Such surfactants mone, fluthiacet-methyl, fomesafen, halosulfuron, haloxy include amines or quaternary ammonium salts having the fop-methyl, hexazinone, imaZoSulfuron, indanofan, isoprotu formula: ron, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, 40 lenacil, linuron, mefenacet, metamitron, metaZachlor, metha benzthiaZuron, methyldymron, metobenzuron, metobromu ron, metolachlor, metoSulam, metoxuron, metribuzin, met 2 (24) R Sulfuron, molinate, monolinuron, naproanilide, M napropamide, naptalam, neburon, nicosulfuron, norflurazon, R-N V 45 orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, R3 O oxyfluorfen, pebulate, pendimethalin, pentanochlor, pentox (25) aZone, phenmedipham, piperophos, pretilachlor, primisulfu ron, prodiamine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyZa R-N-R 50 mide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyra R4 O Zolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, 2 (26) pyridate, pyriminobac-methyl, quinclorac, quinmerac, quiza R / lofop-ethyl, rimsulfuron, Sethoxydim, siduron, simazine, RO-(RO)-R-N simetryn, Sulcotrione, SulfentraZone, Sulfometuron, Sulfosul V 55 furon, tebutam, tebuthiuron, terbacil, terbumeton, terbuthyla R3 or zine, terbutryn, thenylchlor, thifensulfuron, thiobencarb, tio 2 (27) R carbazil, tralkoxydim, triallate, triasulfuron, tribenuron, trietazine, trifluralin, triflusulfuron and vernolate. RO-(R6O)-R-N'-R A Another ingredient that can optionally be added to the 60 glyphosate herbicidal compositions or formulations of the R3 present invention to further improve the herbicidal effective ness and related herbicidal properties is a di-carboxylic acid wherein R' is linear or branched alkyl or aryl having from or salt of a di-carboxylic acid. Suitable di-carboxylic acids about 4 to about 16 carbon atoms, R is hydrogen, methyl, that may be added to the herbicidal compositions or formu ethyl, or -(CH2CH2O), H, R is hydrogen, methyl, ethyl, or 65 lations comprising glyphosate or a salt or ester thereof and a -(CH2CH2O), H wherein the sum of xandy is not more than Surfactant as described herein include, for example, Oxalic about 5; R is hydrogen or methyl; R in each of the n (RO) acid, malonic acid, Succinic acid, glutaric acid, maleic acid, US 8,586,504 B2 31 32 adipic acid, and fumaric acid, and combinations or mixtures V. FORMULATIONS thereof, with oxalic acid being preferred. Also, in addition to, or in place of the di-carboxylic acid, salts of the aforemen The herbicidal compositions of the invention can be pre tioned di-carboxylic acids may be incorporated into the her pared on site by the end-user shortly before application to the bicidal formulations of the present invention to improve her foliage of the vegetation to be killed or controlled by mixing bicidal performance. Suitable salts include, for example, in an aqueous Solution (i) glyphosate or a herbicidal deriva alkali metal salts such as potassium salts, alkanolamine salts tive thereof, (ii) a pyridine analog, Such as triclopyr, or a and lower alkylamine salts. Preferred salts include potassium derivative thereof, and (iii) a suitable surfactant. Such com oxalate, dipotassium oxalate, sodium oxalate, disodium positions are typically referred to as "tank-mix' composi oxalate, diammonium oxalate, diethanolamine oxalate, dim 10 tions. Typically, herbicidal compositions of the present inven ethylamine oxalate, alkanolamine salts of oxalic acid, and tion that are ready to be applied directly to foliage can be lower alkylamine salts of oxalic acid. made with a glyphosate concentration as described elsewhere Formulations containing a di-carboxylic acid Such as herein. Additionally, Such herbicidal compositions can be oxalic acid or a di-carboxylic acid salt Such as potassium made with a triclopyr, or some other pyridine analog, at a oxalate, typically contain a Sufficient amount of di-carboxylic 15 concentration also as described elsewhere herein. However, it acid/di-carboxylic acid salt to enhance the resulting efficacy is to be noted that one skilled in the art will recognize that of the herbicidal formulation. The weight ratio of total sur various factors influence the application rate of glyphosate factant to carboxylic acid/carboxylic acid salt may be, for and, for example, triclopyr (or another pyridine analog), example, from about 1:1 to about 50:1, about 5:1 to about required for a desired result. As a result, the concentration of 40:1, or even about 5:1 to about 20:1. This ratio of total Such compositions may be other than as described herein Surfactant to carboxylic acid/carboxylic acid salt may signifi without departing from the scope of the present invention. cantly enhance the herbicidal performance of the resulting Alternatively, the herbicidal compositions of the invention herbicidal formulation. may be provided to the end-user already formulated, either at The di-carboxylic acid or salt thereof which can be added the desired dilution for application (i.e., “ready-to-use” com to herbicidal formulations of the present invention to improve 25 positions) or requiring dilution, dispersion, or dissolution in efficacy are suitable for use with glyphosate, or salts thereof. water by the end-user (i.e., “concentrate compositions, Suitable glyphosate salts include those listed above. Such as wherein the glyphosate concentration is at least about 50 for example the isopropylamine salt, the potassium salt, and grams (a.e.) per liter). Such preformulated concentrates can the trimethylammonium salt. be liquids or particulate Solids. In this regard it is to be noted that U.S. patent application 30 With respect to the particulate solids, or dry formulations, Ser. No. 09/988,353 (entitled Pesticide Compositions Con of the present invention, it is to be noted that these may be in taining Oxalic Acid and published on Sep. 5, 2002 under the form of powders, pellets, tablets or granules. These dry Publication No. US-2002-0123430-A1) is incorporated formulations are typically dispersed or dissolved into water herein by reference, as well as U.S. patent application Ser. prior to use. Preferably, there are no substantially water No. 10/653,332 (entitled Process for the Preparation of a Dry 35 insoluble constituents present at substantial levels in the such Pesticidal Composition Containing a Dicarboxylate Compo formulations such that the formulations are substantially nent and filed on Sep. 2, 2003) and U.S. patent application water soluble. Dry water-soluble or water-dispersable formu Ser. No. 10/653,047 (entitled Pesticidal Compositions Con lations of the present invention typically comprise the same taining Dicarboxylic Acids and filed on Aug. 29, 2003). ratios of glyphosate to triclopyr (G:T), or more generally the Yet another ingredient that can optionally be added to one 40 same ratios of glyphosate to pyridine analog, and glyphosate or more of the compositions of the present invention is a fatty to surfactant (G:S), as described elsewhere herein. With acid (e.g., a Cs to C fatty acid). For example, in at least one respect to the load of the composition ingredients (i.e., gly embodiment the present invention is directed to a composi phosate, triclopyr, or other pyridine analog, and Surfactant), tion (e.g., a Solid or liquid concentrate, or alternatively a as well as the particular ingredients themselves, it is to be ready-to-use composition) comprising glyphosate (or a 45 noted that the selection of these for a given application may be derivative thereof), triclopyr or other pyridine analog (or a determined in view of commercial consideration, and using derivative thereof), a pelargonic acid (or nonanoic acid) or means, known in the art. derivative thereof, and a Surfactant, such as a linear alcohol In dry formulations of the present invention, the glyphosate ethoxylate. itself may provide the support for other formulation constitu Excipient ingredients other than the above-defined surfac 50 ents, or there may be additional inert ingredients which pro tant component can optionally be present in a composition of vide Such support. One example of an inert Supportingredient the invention, so long as the cloud point and non-crystalliza that may be used in accordance with the present invention is tion properties of the composition remain in accordance with ammonium sulfate. It will be recognized by one skilled in the the invention. Such additional excipient ingredients may art that as used herein, the term “dry” does not imply that dry include conventional formulation additives such as dyes, 55 formulations of the present invention are 100% free of water. thickeners, crystallization inhibitors, antifreeze agents (e.g., Typically, dry formulations of the present invention comprise glycols, such a ethylene glycol), foam moderating agents from about 0.5% to about 5% (by weight) water. It is preferred (e.g., AntifoamTM or Y-14088 AntifoamTM, both available that the dry formulations of the present invention contain less from Crompton Corporation), antidrift agents, compatibiliz than about 1% (by weight) water. Additionally, it is preferred ing agents, antioxidants (e.g., ascorbic acid and sodium 60 for at least some embodiments that the particulate solid exhib sulfite, in order for example to prevent the formation of a its a dissolution rate of not more than about 5 minutes, about nitrosamine), other co-solvents (e.g., N-methylpyrrolidone, 4 minutes, about 3 minutes, about 2 minutes, or even about 1 DMSO, DMF, propylene carbonate, or ethylene glycol), or minute. Some other agent added to lessen or overcome antagonism Dry, water soluble or water dispersable formulations in associated with hardwater (e.g., ammonium Sulfate, EDTA or 65 accordance with the present invention can be produced by any a polymeric water conditioner, Such as a polyacrylic acid), process known in the art, including spray drying, fluid-bed etc. agglomeration, pan granulation, or extrusion. In dry formu US 8,586,504 B2 33 34 lations, glyphosate may be present as a salt, or as an acid. the liquid concentrate or the addition of water to the particu Formulations containing glyphosate acid may optionally con late Solid concentrate. However, the term “aqueous, as used tain an acid acceptor Such as an ammonium or alkali metal herein, is not intended to exclude the presence of some Small carbonate or bicarbonate, ammonium dihydrogen phosphate amount of nonaqueous solvent, so long as the predominant or the like so that upon dissolution or dispersion in water by Solvent present, other than for example the glycol or glycol the user a water Soluble salt of glyphosate is produced. ester component of the Surfactant composition, is water. Also embraced by the present invention are liquid concen trate formulations having an aqueous phase wherein glypho VI. APPLICATION sate is present predominantly in the form of a salt, and a non-aqueous phase optionally containing a second herbicidal 10 Generally speaking, the present invention is additionally active ingredient that is relatively water-insoluble. Such for directed to a method of for killing or controlling weeds or mulations illustratively include emulsions (including macro unwanted vegetation which comprises the steps of diluting a and microemulsions, water-in-oil, oil-in-water and water-in liquid concentrate in a convenient amount of water to form a oil-in-water types), Suspensions and Suspoemulsions. The tank mix and applying a herbicidally effective amount of the non-aqueous phase can optionally comprise a microencapsu 15 tank mix to the foliage of the weeds or unwanted vegetation. lated component, for example a microencapsulated herbicide. Similarly included in the invention is the method of killing or Informulations of the invention having a non-aqueous phase, controlling weeds or unwanted vegetation comprising the the concentration of glyphosate a.e. in the composition as a steps of diluting a solid particulate concentrate in a conve whole is nonetheless within the ranges recited herein for nient amount of water to form a tank mix and applying a aqueous concentrate formulations. herbicidally effective amount of the tank mix to the foliage of Illustrative water-insoluble herbicides that can be used in the weeds or unwanted vegetation. Such formulations include acetochlor, aclonifen, alachlor, The herbicidal composition of the present invention is ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azim applied to plants at a rate Sufficient to give the desired bio sulfuron, benfluralin, benfuresate, bensulfuron-methyl, ben logical effects: control of plant growth and early visual symp sulide, benzofenap, bifenox, bromobutide, bromofenoxim, 25 toms of treatment. The amount of glyphosate and triclopyr, or butachlor, butamifos, butralin, butroxydim, butylate, cafens other pyridine analog, applied to plants in combination gen trole, carbetamide, carfentraZone-ethyl, chlomethoxyfen, erally provides a herbicidally-effective amount of the herbi chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitro cides. The amount of glyphosate and triclopyr, or other pyri fen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal dine analogy, applied to plants further is sufficient to provide dimethyl, chlorthiamid, cinmethylin, cinosulfuron, 30 early visual symptoms of plant treatment without signifi clethodim, clodinafop-propargyl, clomaZone, clomeprop, cantly reducing the desired biological effect of the glypho cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, sate. These application rates are usually expressed as amount cycloxydim, cyhalofop-butyl, daimuron, desmedipham, des of glyphosate per unit area treated, e.g. grams per hectare metryn, dichlobenil, diclofop-methyl, diflufenican, dimefu (g/ha). What constitutes a “desired effect varies according to ron, dimepiperate, dimethachlor, dimethametryn, dimethena 35 the standards and practice of those who investigate, develop, mid, dinitramine, dinoterb, diphenamid, diuron, EPTC, market and use compositions. Typically, the amount of the esprocarb, ethal fluralin, ethametsulfuron-methyl, ethofume composition applied per unit area to give 85% control of a sate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenu plant species as measured by growth reduction or mortality is ron, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchlo often used to define a commercially effective rate. Early ralin, flumetSulam, flumiclorac-pentyl, flumioxazin, 40 visual symptoms of treatment typically appear no later than fluometuron, fluorochloridone, fluoroglycofen-ethyl, about 4 days after treatment, preferably no later than about 3 flupoxam, flurenol, fluridone, flurtamone, fluthiacet-methyl, days after treatment, more preferably no later than about 2 fomesafen, halosulfuron, haloxyfop-methyl, hexaZinone, days after treatment, and still more preferably no later than imaZoSulfuron, indanofan, isoproturon, isouron, isoxaben, about 1 day after treatment. isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, mefen 45 The selection of application rates that are herbicidally acet, metamitron, metaZachlor, methabenzthiazuron, meth effective for a composition of the invention is within the skill yldymron, metobenzuron, metobromuron, metolachlor, of the ordinary agricultural scientist. Those of skill in the art metoSulam, metoXuron, metribuzin, metSulfuron, molinate, will likewise recognize that individual plant conditions, monolinuron, naproanilide, napropamide, naptalam, nebu weather and growing conditions, as well as the specific active ron, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiar 50 ingredients and their weight ratio in the composition, will gyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate, pen influence the degree of herbicidal effectiveness achieved in dimethalin, pentanochlor, pentoxaZone, phenmedipham, practicing this invention. With respect to the use of glypho piperophos, pretilachlor, primisulfuron, prodiamine, prome sate compositions, much information is known about appro ton, prometryn, propachlor, propanil, propaquizafop, pro priate application rates. Over two decades of glyphosate use pazine, propham, propisochlor, propyZamide, prosulfocarb, 55 and published studies relating to Such use have provided prosulfuron, pyraflufen-ethyl, pyrazolynate, pyrazosulfuron abundant information from which a weed control practitioner ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-me can select glyphosate application rates that are herbicidally thyl, quinclorac, quinmerac, quizalofop-ethyl, rimsulfuron, effective on particular species at particular growth stages in Sethoxydim, siduron, Simazine, simetryn, Sulcotrione, Sulfen particular environmental conditions. traZone, Sulfometuron, Sulfo Sulfuron, tebutam, tebuthiuron, 60 The herbicidal spray compositions included in the present terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, invention can be applied to the foliage of the plants to be thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, trial treated through any of the appropriate methods that are well late, triasulfuron, tribenuron, trietazine, trifluralin, triflusul known to those having skill in the art. However, in one furon and Vernolate. embodiment, the herbicidal composition is applied using It is to be noted that the herbicidal spray compositions of 65 means other than a helicopter, stated another way, in at least the present invention are applied as aqueous Solutions or Some embodiments the present invention is directed to meth dispersions, whether they result from the further dilution of ods wherein the herbicidal composition is applied using non US 8,586,504 B2 35 36 aerial means (i.e., ground application techniques. Such as a Plant treatment compositions can be prepared simply by hand sprayer, rope-wick, etc.) or using a fixed-wing aircraft. diluting a concentrate composition of the invention in water. Particularly important annual dicotyledonous plant species Application of plant treatment compositions to foliage is for control of which a composition of the invention can be preferably accomplished by spraying, using any conventional used are exemplified without limitation by Velvetleaf 5 means for spraying liquids, such as spray nozzles, atomizers (Abutilon theophrasti), pigweed (Amaranthus spp.), button or the like. Compositions of the invention can be used in weed (Borreria spp.), oilseed rape, canola, indian mustard, precision farming techniques, in which apparatus is etc. (Brassica spp.), commelina (Commelina spp.), filaree employed to vary the amount of pesticide applied to different (Erodium spp.), Sunflower (Helianthus spp.), morningglory parts of a field, depending on variables Such as the particular (Ipomoea spp.), kochia (Kochia scoparia), mallow (Malva 10 plant species present, Soil composition, etc. In one embodi spp.), wild buckwheat, Smartweed, etc. (Polygonum spp.), ment of Such techniques, a global positioning system oper purslane (Portulaca spp.), russian thistle (Salsola spp.), Sida ated with the spraying apparatus can be used to apply the (Sida spp.), wild mustard (Sinapis arvensis) and cocklebur desired amount of the composition to different parts of a field. (Xanthium spp.). 15 Particularly important annual monocotyledonous plant VII. DEFINITIONS species for control of which a composition of the invention can be used are exemplified without limitation by wild oat The terms “hydrocarbon' and “hydrocarbyl as used (Avena fatua), carpetgrass (Axonopus spp.), downy brome herein describe organic compounds or radicals consisting (Bromus tectorum), crabgrass (Digitaria spp.), barnyardgrass exclusively of the elements carbon and hydrogen. These moi (Echinochloa crus-galls), goosegrass (Eleusine indica), eties include alkyl, alkenyl, alkynyl, and aryl moieties. These annual ryegrass (Lolium multiflorum), rice (Oryza sativa), moieties also include alkyl, alkenyl, alkynyl, and aryl moi ottochloa (Ottochloa nodosa), bahiagrass (Paspalum eties substituted with other aliphatic or cyclic hydrocarbon notatum), canarygrass (Phalaris spp.), foxtail (Setaria spp.), groups, such as alkaryl, alkenaryland alkynary1. Unless oth wheat (Triticum aestivum) and corn (Zea mays). 25 erwise indicated, these moieties preferably comprise 1 to 30 Particularly important perennial dicotyledonous plant spe carbon atoms. cies for control of which a composition of the invention can be The term “hydrocarbylene' as used herein describes radi used are exemplified without limitation by mugwort (Artemi cals joined at two ends thereof to other radicals in an organic sia spp.), milkweed (Asclepias spp.), canada thistle (Cirsium compound, and which consist exclusively of the elements arvense), field bindweed (Convolvulus arvensis) and kudzu 30 carbon and hydrogen. These moieties include alkylene, alk (Pueraria spp.). enylene, alkynylene, and arylene moieties. These moieties Particularly important perennial monocotyledonous plant also include alkyl, alkenyl, alkynyl, and aryl moieties substi species for control of which a composition of the invention tuted with other aliphatic or cyclic hydrocarbon groups. Such can be used are exemplified without limitation by brachiaria as alkaryl, alkenaryl and alkynary1. Unless otherwise indi (Brachiaria spp.), bermudagrass (Cynodon dactylon), yellow 35 cated, these moieties preferably comprise 1 to 30 carbon nutsedge (Cyperus esculentus), purple nutsedge (C. rotun atOmS. dus), quackgrass (Elymus repens), lalang (Imperata cylin The “substituted hydrocarbyl moieties described herein drica), perennial ryegrass (Lolium perenne), guineagrass are hydrocarbyl moieties which are substituted with at least (Panicum maximum), dallisgrass (Paspalum dilatatum), reed one atom other than carbon, including moieties in which a (Phragmites spp.), johnsongrass (Sorghum halepense) and 40 carbon chain atom is substituted with a hetero atom such as cattail (Tipha spp.). nitrogen, oxygen, silicon, phosphorous, boron, Sulfur, or a Other particularly important perennial plant species for halogen atom. These Substituents include halogen, heterocy control of which a composition of the invention can be used clo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected are exemplified without limitation by horsetail (Equisetum hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, cyano, spp.), bracken (Pteridium aquilinum), blackberry (Rubus 45 thiol, acetal, sulfoxide, ester, thioester, ether, thioether, spp.) and gorse (Ulex europaeus). hydroxyalkyl, urea, guanidine, amidine, phosphate, amine If desired, the user can mix one or more adjuvants with a oxide, and quaternary ammonium salt. composition of the invention and the water of dilution when The “substituted hydrocarbylene' moieties described preparing the application composition. Such adjuvants can herein are hydrocarbylene moieties which are substituted include additional Surfactant and/or an inorganic salt such as 50 with at least one atom other than carbon, including moieties in ammonium sulfate with the aim of further enhancing herbi which a carbon chain atom is substituted with a hetero atom cidal efficacy. However, under most conditions a herbicidal Such as nitrogen, oxygen, silicon, phosphorous, boron, Sulfur, method of use of the present invention gives acceptable effi or a halogen atom. These Substituents include halogen, het cacy in the absence of Such adjuvants. erocyclo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, pro In a particular contemplated method of use of a composi 55 tected hydroxy, ketal, acyl, acyloxy, nitro, amino, amido, tion of the invention, the composition, following dilution in cyano, thiol, acetal, Sulfoxide, ester, thioester, ether, thioet water, is applied to foliage of crop plants genetically trans her, hydroxyalkyl, urea, guanidine, amidine, phosphate, formed or selected to tolerate glyphosate, and simultaneously amine oxide, and quaternary ammonium salt. to foliage of weeds or undesired plants growing in close Unless otherwise indicated, the alkyl groups described proximity to such crop plants. This method of use results in 60 herein are preferably lower alkyl containing from one to 18 control of the weeds or undesired plants while leaving the carbon atoms in the principal chain and up to 30 carbon crop plants Substantially unharmed. Crop plants genetically atoms. They may be straight or branched chain or cyclic and transformed or selected to tolerate glyphosate include those include methyl, ethyl, propyl, isopropyl. n-butyl, isobutyl, whose seeds are sold by Monsanto Company or under license hexyl, 2-ethylhexyl, and the like. from Monsanto Company bearing the Roundup Ready(R) 65 Unless otherwise indicated, the alkenyl groups described trademark. These include, without restriction, varieties of herein are preferably lower alkenyl containing from two to 18 cotton, soybean, canola, Sugar beet, wheat and corn. carbon atoms in the principal chain and up to 30 carbon US 8,586,504 B2 37 38 atoms. They may be straight or branched chain or cyclic and the remainder of the molecule through a carbon or heteroa include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tom. Exemplary heteroaromatics include furyl, thienyl, hexenyl, and the like. pyridyl, oxazolyl pyrrolyl, indolyl, quinolinyl, or isoquino Unless otherwise indicated, the alkynyl groups described linyl and the like. Exemplary substituents include one or more herein are preferably lower alkynyl containing from two to 18 5 of the following groups: hydrocarbyl, substituted hydrocar carbon atoms in the principal chain and up to 30 carbon byl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, atoms. They may be straight or branched chain and include alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like. cyano, thiol, thioether, thioester, ketal, acetal, ester and ether. The terms “arylas used herein alone or as part of another The term “acyl as used herein alone or as part of another group denote optionally Substituted homocyclic aromatic 10 groups, preferably monocyclic or bicyclic groups containing group, denotes the moiety formed by removal of the hydroxyl from 6 to 12 carbons in the ring portion, Such as phenyl, group from the group —COOH of an organic carboxylic acid, biphenyl, naphthyl, substituted phenyl, substituted biphenyl e.g., RC(O)—, wherein R is R', RO , RRN-, or R'S , or substituted naphthyl. Phenyl and substituted phenyl are the R" is hydrocarbyl, heterosubstituted hydrocarbyl, or hetero more preferred aryl. 15 cyclo and R is hydrogen, hydrocarbyl or substituted hydro The term “aralkyl as used herein denotes a group contain carbyl. ing both alkyl and aryl Structures Such as benzyl. The term “acyloxy, as used herein alone or as part of As used herein, the alkyl, alkenyl, alkynyl, arylandaralkyl another group, denotes an acyl group as described above groups can be substituted with at least one atom other than bonded through an oxygen linkage (-O ), e.g., RC(O)O— carbon, including moieties in which a carbon chain atom is wherein R is as defined in connection with the term “acyl.” Substituted with a hetero atom Such as nitrogen, oxygen, The term "pesticide' includes chemicals and microbial silicon, phosphorous, boron, Sulfur, or a halogenatom. These agents used as active ingredients of products for control of Substituents include hydroxy, nitro, amino, amido, nitro, crop and lawn pests and diseases, animal ectoparasites, and cyano, Sulfoxide, thiol, thioester, thioether, ester and ether, or other pests in public health. The term also includes plant any other substituent which can increase the compatibility of 25 growth regulators, pest repellants, synergists, herbicide the Surfactant and/or its efficacy enhancement in the glypho safeners (which reduce the phytotoxicity of herbicides to crop sate formulation without adversely affecting the storage sta plants) and preservatives, the delivery of which to the target bility of the formulation. may expose dermal and especially ocular tissue to the pesti The terms “halogen' or “halo' as used herein alone or as cide. Such exposure can arise by drift of the pesticide from the part of another group refer to chlorine, bromine, fluorine, and 30 delivery means to the person performing the application of iodine. Fluorine substituents are often preferred in surfactant compounds. the pesticide or being present in the vicinity of an application. Unless otherwise indicated, the term “hydroxyalkyl When a maximum or minimum “average number is includes alkyl groups substituted with at least one hydroxy recited herein with reference to a structural feature such as group, and includes bis(hydroxyalkyl)alkyl, tris(hydroxy 35 oxyethylene units or glucoside units, it will be understood by alkyl)alkyl and poly(hydroxyalkyl)alkyl groups. Preferred those skilled in the art that the integer number of such units in hydroxyalkyl groups include hydroxymethyl ( CH-OH), individual molecules in a Surfactant preparation typically var and hydroxyethyl ( CH-OH), bis(hydroxymethyl)methyl ies over a range that can include integer numbers greater than (—CH(CHOH)), and tris(hydroxymethyl)methyl ( C the maximum or Smaller than the minimum “average num (CHOH)). 40 ber'. The presence in a composition of individual surfactant The term "cyclic” as used herein alone or as part of another molecules having an integer number of Such units outside the group denotes a group having at least one closed ring, and stated range in "average number” does not remove the com includes alicyclic, aromatic (arene) and heterocyclic groups. position from the scope of the present invention, so long as the The terms "heterocyclo” or "heterocyclic” as used herein “average number is within the stated range and other alone or as part of another group denote optionally Substi 45 requirements are met. tuted, fully saturated or unsaturated, monocyclic or bicyclic, Herbicidal effectiveness is one of the biological effects that aromatic or nonaromatic groups having at least one heteroa can be enhanced through this invention. “Herbicidal effec tom in at least one ring, and preferably 5 or 6 atoms in each tiveness,” as used herein, refers to any observable measure of ring. The heterocyclo group preferably has 1 or 2 oxygen control of plant growth, which can include one or more of the atoms, 1 or 2 sulfur atoms, and/or 1 to 4 nitrogenatoms in the 50 actions of (1) killing, (2) inhibiting growth, reproduction or ring, and may be bonded to the remainder of the molecule proliferation, and (3) removing, destroying, or otherwise through a carbon or heteroatom. Exemplary heterocyclo diminishing the occurrence and activity of plants. The herbi include heteroaromatics such as furyl, thienyl, pyridyl, cidal effectiveness data set forth herein report “control as a oxazolyl pyrrolyl, indolyl, quinolinyl, or isoquinolinyl and percentage following a standard procedure in the art which the like, and non-aromatic heterocyclics such as tetrahydro 55 reflects a visual assessment of plant mortality and growth furyl, tetrahydrothienyl, piperidinyl, pyrrolidino, etc. Exem reduction by comparison with untreated plants, made by tech plary substituents include one or more of the following nicians specially trained to make and record Such observa groups: hydrocarbyl, Substituted hydrocarbyl, keto, hydroxy, tions. In all cases, a single technician makes all assessments protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, of percent control within any one experiment or trial. Such aryloxy, halogen, amido, amino, nitro, cyano, thiol, thioester, 60 measurements are relied upon and regularly reported by thioether, ketal, acetal, ester and ether. Monsanto Company in the course of its herbicide business. The term "heteroaromatic' as used herein alone or as part of another group denote optionally Substituted aromatic EXAMPLES groups having at least one heteroatom in at least one ring, and preferably 5 or 6 atoms in each ring. The heteroaromatic 65 The following Examples are provided for illustrative pur group preferably has 1 or 2 oxygenatoms, 1 or 2 sulfur atoms, poses only and are not intended to limit the scope of the and/or 1 to 4 nitrogenatoms in the ring, and may be bonded to present invention. The Examples will permit better under US 8,586,504 B2 standing of the invention and perception of its advantages and TABLE 1.2-continued certain variations of execution. Formulations. Section 1 5 Glyphosate Triclopyr (T); Formulations (G); g/Kg g/Kg: G:T CODE (62% ai) (44% ai) w:w Surfactant wiw;% Aqueous herbicide formulations were generated from com mercially available glyphosate isopropylamine, triclopyr tri- 10 F6Y 290.3 59.9 18:2.66 FSS 3.5 ethylamine and various Surfactants in the ratios indicated in F3Y 290.3 45 18.2 FS5 3.5 Tables 1.1 and 1.2. TABLE 1.1

Formulations: Glyphosate (G); Triclopyr (T); G:T Surf G:Surf CODE gaefL gae/L w:w Surfactant wiv% w:w RUP1 351 ae (30.6%) FS1 11.9 3.0 RUP2 443 ae (37.2%) FS1 9.81 4.5 RU1 27% Roundup FS4 4.11 3.5 FG1 46.3% ae F2M 142 7.71 18.5:1 FS1 4.11 3.5 F1M 142 3.85 18.S.O.S FS1 4.11 3.5 F1C 142 3.85 18.S.O.S FS4 5.4 3.6 F2C 142 7.66 18.5:1 FS4 5.3 3.6 F3M 143 15.4 18.6:2 FS1 4.11 3.5 FSM 7.38 0.72 2O.S:2 FS1 O.21 3.6 F4C 151.3 24.48 18.5:3 FS4 5.7 3.6 F11M 7.38 O.36 2O.S:1 FS1 O.21 3.6 F8M 142 92.5 18.5:12 FS1 4.11 3.5 F9M 142 61.7 18.5:8 FS1 4.11 3.5 F1 OM 142 40.9 18.5:5.3 FS1 4.11 3.5 Glyphosate and triclopyr are expressed as the acid equivalent load (gae/L). The densities of the concentrate formulations are in the range 1.06 to 1.17 g/ml. The ready-to-use formulation has a density of approx. 1,004 iml. FE glyphosatetriclopyr wiw ratio given interms of the acid equivalent weights, The surfactant load is expressed as the weight volume %, i.e. g. 100 ml. The glyphosateisurfactant wiw ratio, i.e., gaelg surfactant per kg of formulation,

TABLE 1.2 TABLE 1.2-continued

Formulations. 40 Formulations. Glyphosate Triclopyr (T); (G); gKg g/Kg: G:T Glyphosate Triclopyr (T); CODE (62% ai) (44% ai) w;w Surfactant w/w;% (G); g/Kg g/Kg: G:T CODE (62% ai) (44% ai) w;w Surfactant w/w;% F14X 290.3 25.5 8:1.13 FS3 5 E. 3. . S. 45 F4y 290.3 67.6 18:3 FSS 3.5 F6X 29O.4 60 8:2.66 FS3 5 F7Y 290.3 90.1 18:4 FS5 3.5 F4X 29O.4 67.6 8:3 FS3 5 F3X 290.3 45 8:2 FS3 5 Glyphosate load expressed as the weight of a standard (62% aiglyphosate) used per 1000 g. The densities of the concentrate formulations are in the range 1.06 to 1.17 g/ml. The F2X 290.3 22.5 8:1 ES3 5 ready-to-use formulation has a density of approx. 1,004 giml. F1X 290.3 11.3 8:O.S FS3 5 50 Triclopyr load expressed as the weight of a standard (44.3% aitriclopyr) used per 1000 g. FOX 290.3 O 8:0 FS3 5 The densities of the concentrate formulations are in the range 1.06 to 1.17 g/ml. The F14M 290.3 25.5 8:1.13 FS1 5 ready-to-use formulation has a density of approx. 1,004 giml. F13M 290.3 51 8:2.25 FS1 5 The glyphosatetriclopyr wiw ratio is given in terms of the % aio ai. F12M 290.3 101 8:4SO FS1 5 The surfactant is expressed as the wiw % i.e., weight of surfactant standard per 100g. F6M 29O.4 60 8:2.66 FS1 5 FAM 29O.4 67.6 8:3 FS1 5 55 Key to Surfactants: FSM 16.1 2.3 1:0.1 FS1 5 F3M 290.3 45 8:2 FS1 5 1. FS1 surfactant composition is a mixture of tallowamines F1MF2M 290.3 22.511.3 8:18:O.S FS1FS1 5 and phosphate esters, as described in U.S. Pat. No. 5,703, FOM 290.3 O 8:0 FS1 5 O15. . 3. st S; 60 2. FS2 surfactant composition is a mixture of tallowamines F13C 290.3 51 82.25 FS4 5 and phosphate esters, as described in U.S. Pat. No. 5,703, F12C 290.3 101 8:4SO FS4 5 O15. F4C 290.3 67.6 8:3 FS4 5 F3C 290.3 45 8:2 FS4 5 3. FS3 surfactant composition is a mixture of a tallowamine F2C 290.3 22.5 8:1 FS4 5 ethoxylate with other surfactants. F1C 290.3 11.3 8:O.S FS4 5 65 FOC 290.3 O 8:0 FS4 5 4. FS4 is a Cocoamine 5EO. 5. FS5 is a Cocoamine 5EO. US 8,586,504 B2 41 42 Section 2 TABLE 2.1B Stability Test & Results Stability Results. % wtai -20 Example 2.1 5 CODE Triclopyr Surfactant +20° C. 60° C. Stability Test F6X 2.66 FS3 crystals All formulations No layered from freeze layering thaw Materials & Methods: F3X 2 FS3 clear All formulations No Various formulations were maintained at constant tempera- 10 layered from freeze layering ture for a fixed period and monitored for changes in color, thaw homogeneity and appearance after thawing. The formulations F4X 3 FS3 crystals All formulations No were also cycled through temperature extremes i.e., at low yed from freeze layering temperatures of -20°C.O and -5°C.O for the fixed period then F6M 2.66 FS1 crystals All8W formulations No raised to the higher temperatures of 20° C. and 5° C. respec- 15 layered from freeze layering tively and changes monitored. Results for a 4-week study are thaw tabulated below. F3M 2 FS1 clear All formulations No Results: TABLE 2.1A

Stability Results. Temperature Stability Results (4 weeks) Apperance

Formulation % wtai % wtai Surfactant -20+20° C. -5+5°C. after thawing CODE Glyphosate Triclopyr (5%) RT (-19.9°C.) (-6.7° C.) 4.5° C. 60° C. -10° C. to Room Temp.

F12X 8 4...SO FS3 No Color at No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F13X 8 2.25 FS3 No Color at No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F14X 8 1.13 FS3 No Color at No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing FOX 8 O.OO FS3 No Color at No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F12M 8 4...SO FS1 No Xtals No No No Solid, Crystals change 10% change change change crystals remain on (btm) bottom (10%) F13M 8 2.25 FS1 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F14M 8 1.13 FS1 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing FOM 8 O.OO FS1 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F15C 8 6.76 FS4 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F12C 8 4...SO FS4 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F13C 8 2.25 FS4 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing F14C 8 1.13 FS4 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing FOM 8 O.OO FS3 No Color a No No No Solid, No crystals, change bottom change change change crystals homogenous after mixing US 8,586,504 B2 43 44 TABLE 2.1 B-continued greenhouse with Sub-irrigation. About one week after emer gence, seedlings were thinned as needed, including removal Stability Results. of any unhealthy or abnormal plants, to create a uniform 0.% wtai -20 series of test pots. CODE Triclopyr Surfactant +20° C. 60° C. 5 The plants were maintained for the duration of the test in the greenhouse where they received a minimum of 14 hours of ayered from freeze layering light per day. If natural light was insufficient to achieve the F4M 3 FS1 crystals Simulations No daily requirement, artificial light with an intensity of approxi ayered from freeze layering mately 475 microeinsteins was used to make up the differ 8W 10 ence. Exposure temperatures were not precisely controlled F6Y 2.66 FSS clear All formulations No but averaged about 27°C. during the day and about 21° C. y rom Ireeze layering during the night. Plants were Sub-irrigated throughout the test F3Y 2 FS5 clear All formulations No to ensure adequate Soil moisture levels. ayered from freeze layering Pots were assigned to different treatments in a randomized 8W 15 experimental design with 6 replications. A set of pots was left F4Y 3 FS5 clear Allayered formulations Irom Ireeze Noayering untreated as a reference against which effects of the treat 8W ments could later be evaluated. F7Z 4 FSS - crystals All formulations No Application of glyphosate compositions was made by NMP ayered from freeze layering spraying with a track sprayer fitted with a flateven 8008E 8W 20 nozzle calibrated to deliver a spray volume of 1348 liters per hectare (1/ha) at a pressure of 165 kilopascals (kPa). After treatment, pots were returned to the greenhouse until ready Section 3 for evaluation. Treatments were made using dilute aqueous compositions. Greenhouse Test & Results 25 For evaluation of herbicidal effectiveness, all plants in the test were examined by a single practiced technician, who Objective: Greenhouse study of potential Roundup Brush- recorded percent control, a visual measurement of the effec killer formulations on Red Maple and Red Oak. tiveness of each treatment by comparison with untreated Materials & Methods: Standard post emerge herbicide appli- plants. Control of 0% indicates no effect, and control of 100% cation procedures were used, such the procedure described 30 indicates that all of the plants are completely dead. Control of below. The herbicide formulations tested are listed in Table 85% or more is in most cases considered acceptable for nor 3.1 below. Additional information is available in Tables 1.1 mal herbicide use; however in greenhouse tests such as those and 1.2. for the examples it is normal to apply compositions at rates Seeds of the plant species indicated were planted in 3.5 in which give less than 85% control, as this makes it easier to square pots in a Soil mix which was previously steam steril- 35 discriminate among compositions having different levels of ized and prefertilized with a 14-14-14 NPK slow release effectiveness. The reported '% control values represent the fertilizer at a rate of 100 g/ft. The pots were placed in a average for all replicates of each treatment. TABLE 3.1

Glyphosate Formulations for Greenhouse Testing:

ww.9% Wiw % Amt Other Formulation Glyph. Glyph. Amt.,g Salt Surfact. active; Triclopyr Code 8t ai ae/L Form Surfact. wiw % Triclopyr amt% ai

F3X 3.34 18.00 143.70 IPA FS3 5.0% Hammer 2.0% F2X 3.34 18.00 14327 IPA FS3 5.0% Hammer 1.0% F1X 3.34 18.00 143.07 IPA FS3 5.0% Hammer O.5% FOX 3.34 18.OO 142.78 IPA FS3 S.0% F3M 3.34 18.00 143.60 IPA FS1 5.0% Hammer 2.0% F2M 3.34 18.00 143.18. IPA FS1 5.0% Hammer 1.0% F1M 3.34 18.OO 142.96 IPA FS1 5.0% Hammer O.5% FOM 3.34 18.OO 142.75 IPA FS1 S.0% F4C 3.34 18.00 143.69 IPA FS4 5.0% Hammer 3.0% F3C 3.34 18.00 143.26 IPA FS4 5.0% Hammer 2.0% F2C 3.34 18.OO 142.84 IPA FS4 5.0% Hammer 1.0% F1C 3.34 18.OO 142.63 IPA FS4 5.0% Hammer O.5% FOC 3.34 18.OO 142.83 IPA FS4 S.0%

COMMERCIAL PRODUCTS ACTIVE % Ai

RUPBSKCONC GLYPH 27.0 BBG TRICL 8.0 ENF BSK CONC TRICL 8.8 US 8,586,504 B2 45 46 Results: TABLE 32A

GREENEHOUSE STUDY OF POTENTIAL ROUNDUP BRUSHKILLER FORMULATIONS ON RED MAPLE AND RED OAK

% CTRL SDAT % CTRL SDAT

CHEMICAL FORM MDXRATE MAPLE MAPLE MAPLE MAPLE OAK OAK OAK TRT FORMULN DESIG OZ.GAL REP 1 REP 2 REP 3 AVE. REP 1 REP 2 AVE.

1 F3X SL 6 SS.O 3 O.O 65.O SO.O O.O 3 O.O 15.O 2 F2X SL 6 3O.O 20.O 400 3O.O O.O 40.O 20.O 3 F1X SL 6 2O.O SO.O 20.O 3O.O 4S.O 70.O ST.S 4 FOX SL 6 S.O S.O. 10.O 6.7 S.O S.O S.O 5 F3M SL 6 SS.O 70.O 70.O 65.0 4S.O. 10.O 27.5 6 F2M SL 6 2S.O 3S.O 70.O 43.3 1OO 100 10.O 7 F1M SL 6 3O.O SO.O 2SO 3S.O S.O 3 O.O. 17.5 8 FOM SL 6 40.O 3S.O 3O.O 3S.O S.O 20.O. 12.5 9 F4C SL 6 SS.O SS.O 650 S8.3 8O.O. 10.O 45.0 10 F3C SL 6 SS.O SS.O 40.O SO.O S.O 20.O. 12.5 11 F2C SL 6 40.O SO.O 350 41.7 7S.O S.O 400 12 F1C SL 6 3S.O 3S.O 20.O 3O.O S.O. 10.O 7.5 13 FOC SL 6 1S.O S.O. 10.O 1O.O O.O S.O 2.5 14 RUP BSK CONC SL 6 3O.O 25.0 3O.O 28.3 O.O 70.O 3S.O 1S ORTHO BBG SL 4 6O.O 7S.O 200 S1.7 4S.O SO.O 47.5 16 ENF BSK CONC SL 4 2S.O 25.0 3O.O 26.7 10.O 5.O 7.5 17 UNTREATED O.O O.O O.O O.O O.O O.O O.O CONTROL

TABLE 3.2B

GREENEHOUSE STUDY OF POTENTIAL ROUNDUP BRUSHKILLER FORMULATIONS ON RED MAPLE AND RED OAK

% CTRL 21 DAT % CTRL 21 DAT

CHEMICAL FORM MDXRATE MAPLE MAPLE MAPLE MAPLE OAK OAK OAK TRT FORMULN DESIG OZ.GAL REP 1 REP 2 REP 3 AVE. REP 1 REP 2 AVE.

1 F3X SL 6 OO.O OO.O OO.O OO.O 95.0 OO.O 97.5 2 F2X SL 6 OO.O OO.O OO.O OOO 100.0 OOO 10O.O 3 F1X SL 6 OO.O OO.O OO.O OOO 100.0 OOO 10O.O 4 FOX SL 6 OO.O OO.O OOOO 100.0 80.0 OO.O 90.0 5 F3M SL 6 OO.O OO.O OO.O OOO 80.O.O 100.0 90.0 6 F2M SL 6 OO.O OO.O OO.O OO.O 95.0 95.0 95.0 7 F1M SL 6 OO.O OO.O OO.O OOO 99.0 99.0 99.0 8 FOM SL 6 OO.O OO.O OO.O OO.O 7S.O 88.0 81.5 9 F4C SL 6 OO.O OO.O OOOO 100.0 88.0 OO.O. 94.O 10 F3C SL 6 OO.O OOOO OOOO 100.0 90.0 OO.O 95.0 11 F2C SL 6 OO.O OOOO OO.O OOO 100.0 98.0 99.0 12 F1C SL 6 OO.O OO.O OO.O OOO 99.0 99.0 99.0 13 FOC SL 6 OO.O 95.0 88.0 94.3 450 OO.O 72.5 14 RUP BSK CONC SL 6 OO.O OO.O OO.O OOO 100.0 95.0 97.5 1S ORTHO BBG SL 4 OO.O OO.O OO.O OOO 100.O.O 100.0 1OO.O 16 ENF BSK CONC SL 4 OO.O OO.O OO.O OOO 100.0 OOO 10O.O 17 UNTREATED O.O O.O O.O O.O O.O O.O O.O CONTROL

Discussion: failed to provide 100% control. The oak control went up as the 5 DAT: The maples exhibited more injury as the triclopyr triclopyr level decreased. The lowest level of triclopyr was the level went up. The oaks responded more inconsistently than best on oak and all triclopyr-containing formulations the maples in this regard. Formulation F1X provided the best 55 appeared to perform better than glyphosate alone. Tallowa control of oak at this rating. Only formulations F3M and F4C provided more injury than Ortho Brush-B-Gone (BBG) on mine formulation FS3 seemed to be the best surfactant on maple. The surfactant FS4 proved to be slightly better overall oak. than did the tallowamine formulation FS1. The other tallowa Sections 4/5 mine FS3 was consistently weaker than both other surfac 60 tantS. The current Roundup 27% brushkiller formulation failed Field Test & Results to provide the same level of injury as that of the Brush-B- Gone product. It did, however, outperform Enforcer (ENF) on Example 4.1 both species. 65 21 DAT: The maples proved to be much easier to control Objective: Demonstrate that F3M and F5M formulations than the oaks at this evaluation time. Only FOC (no triclopyr) provide commercially acceptable weed control. US 8,586,504 B2 47 48 Materials and Methods: A Ready-To-Use F5M and con during June through August. All brush species were well centrate F3M brush killer formulations were evaluated. F5M established and exhibiting complete foliation of leaf tissue at RTU is constructed as 1% glyphosate, isopropylamine salt the time of treatment. and 0.10% triclopyr, triethylamine salt, while F3M concen Each test was established using a randomized complete tration formulation is constructed as 18% ai. glyphosate and 5 block design (RCBD) with each of the formulations being 2% a.i. triclopyr. applied to 3, 15 ft plots. Equal volumes of formulation were applied to each plot either with a RTUPull n Spray(R) sprayer Nine field trials were conducted at various geographic used to apply, the RTU F5M formulation a Roundup(R) Her regions in the U.S. to evaluate poison ivy, poison oak, kudzu, bicide Sprayer to apply the concentrate F3M formulation. and multiflora rose control when treated with F5M and F3M. 10 F5M was applied based on 1 gal of solution treats 300 sq ft (equivalent to 145 gallons per acre) and the standard applica TABLE 4.1.1 tion volume for a spray to wet treatment. F3M concentrate Location and Number of Brush Tests by Species. formulation was applied at a rate of 6 oZ/gallon spray to wet. Brush control ratings were evaluated at 1, 3, 21 and 90 days Primary Species Tested 15 after treatment (DAT). Visual assessment of formulation effi Poison Poison Multiflora cacy was assessed on a 0 to 100% scale based on brush control Geographic Ivy Oak Rose Kudzu (chorosis, necrosis and kill) compared to the untreated plots. Region State Number of tests Values close to 0% indicate no visual presence of brush dam Mid-West Illinois age by a formulation, while values approaching 100% indi Ohio cate complete kill of a brush species compared to untreated Central Missouri plots. In addition, values greater than 80% control indicate South Alabama that a product is Supplying the industry standard commer Mississippi cially acceptable weed/brush control. West California To quantify differences in percent brush control among 25 formulations for each weed species by observation date, Dun The brush tests were conducted on preexisting brush infes can's multiple range test was applied and evaluated at P=0.05. tations typically located along and within fence and tree lines Results: TABLE 412

F3M and F5M gave commercial control up to 90 DAT on Poison Ivy and Poison Oak.

Poison Ivy Poison Oak DAT

21 90 1 21 90 Trt. Formuln. % Control

6a 36a 100a 100a Oa 1Ob 85a 1OOa 100a 7a. 36a 1OOa 100a Oa. 23a 100a 100a Untreated Ob Ob Oc Ob Ob Oa. Oc Ob Ob Check

Means followed by same letter, for each weed species, do not significantly differ (P = 0.05, Duncan's multiple range test)

TABLE 413 F3M and F5M gave commercial control up to 90 DAT on Multiflora Rose and Kudzu.

Multiflora Rose Kudzu DAT

21 90 1 21 90 Trt. Formuln. % Control

78a. 93a 100a 11a 90a 88a. 80a 94a 100a 10a 93a 90a Untreated Ob Ob Ob Ob Ob Ob Check

Means followed by same letter, for each weed species, do not significantly differ (P = 0.05, Duncan's multiple range test) US 8,586,504 B2 49 50 TABLE 414 Example 4.3 F3M and F5M gave commercial control up to 90 DAT on all brush tests combined. Evaluation on Kudzu Overall Brush DAT Materials & Methods: Field evaluations of experimental for mulations tabulated below were conducted on brush species 1 3 7 21 90 (Kudzu Roadside) in Mississippi. Trt. Formuln. % Control

1 F3M 6a 34b 86a 96a 98a. 10 TABLE 4.3.1 2 FSM 7a. 39a 90a 97a 98a. 3 Untreated Ob Oc Ob Ob Ob Formulation % ai Triclopyr Chk Code % ai Gly IPA TEA Surfactant % Surfactant Four brush species were tested poison oak, poison ivy, multiflora rose, and kudzu across 9 F2M 18 1 FS1 5 brush tests F1M 18 O.S FS1 5 Means followed by same letter, for each weed species, do not significantly differ 15 F1C 18 O.S FS4 5 (P = 0.05, Duncan's multiple range test) F2C 18 1 FS4 5 F3M 18 2 FS1 5 Discussion: F4C 18 3 FS4 5 F5M and F3M provided commercial control of tough to con BSK or RU1 27 O FS1 trol brush. At 90 DAT brush control for all species tested BBG O O ranged between 90 and 100% control (Tables 4.2.1 through 4.3.4). F5M and F3M tested at various regions and brush Results: species will deliver effective weed control of unwanted veg etation up to 90DAT. TABLE 4.3.2 25 Example 4.2 Form Rate f Trt # Code OZ gal 7 DAT: 10 DAT: * 30 DAT: *

Evaluation on Poison Ivy 1 BSK 6 41.7 83.3 100 2 F1M 6 36.7 8O 100 Objectives: Evaluate various formulations on Poison Ivy. 3 F2M 6 45 87 100 Materials & Methods: Formulations tabulated below were 30 4 F4C 6 46.7 78.3 100 5 F3M 6 36.7 73.3 98.3 field tested for 14 days in September to October at Clemson, 6 BBG 4. 33.3 23.3 73.3 S.C. SeeTables 1.1 and 1.2 for description of product formu 7 BBG. -- 43 40 30 85 lations. FS1 Results: 8 Untreated O O O 35 Check

TABLE 4.2.1 Tabulated values are the mean of 3 tests. Product Form. Rate in oZ1 gallon % injury 14 DAT Poison ivy 1. BSK 6 oz 8O 40 Example 4.4 2. F1M 6 oz 8O 3.F2M 6 oz 91.6 4. F4C 6 oz 100 Field Test at Mississippi i2 5. F3M 6 oz 100 6. BBG 4 oz 70 7. BBG - FS1 4 oz + 3 oz 86.4 Materials & Methods: Evaluations on experimental formula 8. Untreated O 10* 45 tions were conducted on brush species at various locations Check and summarized below (St Louis, Clemson S.C., Missis Untreated Check displayed some natural yellowing due to senescence, or aging, sippi). Results: TABLE 44.1 Summary of Brush Tests Date First Formln DAT

Location Rated Code Formln S 7 10 14 16 30 42 Weed

St Louis uly 18 + 2 90 100 100 Poison Ivy St Louis uly 18 + 1 8O 100 100 Poison Ivy St Louis uly 18 - O.S 70 100 100 Poison Ivy St Louis uly 18 - 3 95 100 100 Poison Ivy St Louis uly 27% Rup 50 95 100 Poison Ivy Brush St Louis uly Brush-B-Gone 85 100 100 Poison Ivy St Louis uly Enforcer 85 100 100 Poison Ivy St Louis uly 18 + 2 85 100 100 Fesci Blue St Louis uly 18 + 1 8O 100 100 Fesci Blue St Louis uly 18 - O.S 85 100 100 Fesci Blue US 8,586,504 B2 51 52 TABLE 4.4.1-continued Summary of Brush Tests

Date First Formln DAT

Location Rated Formln S 7 10 14 16 30 42 Weed

S Louis 8 - 3 90 1OO 100 Fesci Blue S Louis R 27% Rup 50 95 100 Fesci Blue Brush Louis Brush-B-Gon 50 65 70 Fesci Blue Louis t g Enforcer 2O 15 O Fesci Blue Louis 8 + 2 8O 98 100 Golden Rod Louis 8 + 1 65 88 98 Golden Rod Louis 8 - O.S 35 85 100 Golden Rod Louis 4 8 - 3 90 98 98 Golden Rod Louis s 27% Rup 50 95 95 Golden Rod Brush Louis Brush-B-Gon 40 65 65 Golden Rod Louis t g Enforcer 30 75 75 Golden Rod Louis 8 + 2 8O 1OO 100 Fesci Blue Louis 8 + 1 70 1OO 100 Fesci Blue Louis 8 - O.S 50 1OO 100 Fesci Blue Louis 4 C 8 - 3 70 1OO 100 Fesci Blue Louis 27% Rup 85 98 98 Fesci Blue Brush St Louis Brush-B-Gon O O O Fesci Blue St Louis Enforcer O O O Fesci Blue Miss OC e 8 + 2 37 73 98 Kudzu Miss e 8 + 1 45 87 100 Kudzu Miss e 8 - O.S 37 80 100 Kudzu Miss e 8 - 3 47 78 100 Kudzu Miss e 27% Rup 42 83 100 Kudzu Brush Miss Oc O BBG Brush-B-Gon 33 23 73 Kudzu Miss October BBG - Brush-B-Gon- 40 30 85 Kudzu FS1 Clem October RU1 27% Rup 8O Poison Ivy Brush Clem Oc e 8 - O.S 8O Poison Ivy Clem Oc e 8 + 1 91.6 Poison Ivy Clem Oc e 8 - 3 1OO Poison Ivy Clem Oc e Brush-B-Gon 70 Poison Ivy Clem Oc e Brush-B-Gon- 86.4 Poison Ivy

Clem October 8 + 2 1OO Poison Ivy

TABLE 44.2 Grand Brush Test Summary Prod DAT

Location Code Formuln S 7 10 14 16 30 42 Weed

St Louis 8 - O.S 70 OO OO Poison Ivy St Louis 8 - O.S 85 OO OO Fesci Blue St Louis 8 - O.S 35 85 OO Golden Rod St Louis 8 - O.S 50 OO OO Fesci Blue M 8 - O.S 37 80 1OO Kudzu 8 - O.S 8O Poison Ivy 60 96.3 8 + 1 8O OO OO Poison Ivy 8 + 1 8O OO OO Fesci Blue 8 + 1 65 88 98 Golden Rod 8 + 1 70 OO OO Fesci Blue 8 + 1 45 87 1OO Kudzu 8 + 1 91.6 Poison Ivy 74 97 8 + 2 90 OO OO Poison Ivy 8 + 2 85 OO OO Fesci Blue 8 + 2 8O 98 OO Golden Rod 8 + 2 8O OO OO Fesci Blue 8 + 2 37 73 98 Kudzu 8 + 2 100 Poison Ivy 84 99.5 8 - 3 95 OO OO Poison Ivy US 8,586,504 B2 53 54 TABLE 4.4.2-continued Grand Brush Test Summary St Louis F4C 8 - 3 90 1OO 100 Fesci Blue St Louis F4C 8 - 3 90 98 98 Golden Rod St Louis F4C 8 - 3 70 1OO 100 Fesci Blue Miss F4C 8 - 3 47 78 1OO Kudzu Clem F4C 8 - 3 100 Poison Ivy 86 99.5 St Louis RU1 27% Rup 50 95 100 Poison Ivy Brush St Louis RU1 27% Rup 50 95 100 Fesci Blue Brush St Louis RU1 27% Rup 50 95 95 Golden Rod Brush St Louis RU1 27% Rup 85 98 98 Fesci Blue Brush Miss RU1 27% Rup 42 83 1OO Kudzu Brush Clem RU1 27% Rup 8O Poison Ivy Brush 59 95.8 St Louis BBG Brush-B-Gon 85 1OO 100 Poison Ivy St Louis BBG Brush-B-Gon 50 65 70 Fesci Blue St Louis BBG Brush-B-Gon 40 65 65 Golden Rod St Louis BBG Brush-B-Gone O O O Fesci Blue Miss BBG Brush-B-Gone 33 23 73 Kudzu Clem BG Brush-B-Gone 70 Poison Ivy 44 57.5 Miss BBG + Brush-B-Gone- 40 30 85 Kudzu FS1 Clem BBG + Brush-B-Gone- 86.4 Poison Ivy FS1 St Louis ENF Enforcer 85 1OO 100 Poison Ivy St Louis ENF Enforcer 2O 15 O Fesci Blue St Louis ENF Enforcer 30 75 75 Golden Rod St Louis ENF Enforcer O O O Fesci Blue 34 47.5

Product 5 7 10 14 16 30 42 Code DAT DAT DAT DAT DAT DAT DAT Weed BBG 85 1OO 100 Poison Ivy BBG 50 65 70 Fesci Blue BBG 40 65 65 Golden Rod BBG O O O Fesci Blue BBG 33 23 73 Kudzu BBG 70 Poison Ivy RU1 50 95 100 Poison Ivy RU1 50 95 100 Fesci Blue RU1 50 95 95 Golden Rod RU1 85 98 98 Fesci Blue RU1 42 83 100 Kudzu RU1 8O Poison Ivy F3M 90 1OO 100 Poison Ivy F3M 85 1OO 100 Fesci Blue F3M 8O 98 100 Golden Rod F3M 8O 1OO 100 Fesci Blue F3M 37 73 98 Kudzu F3M 100 Poison Ivy

Example 5 TABLE 5 Summary of Test Results 55 Additional Field Test in St. Louis Poison Ivy Total weed Rate in % injury % injury

Formuln oz1 6 12 6 12 Following the procedures set forth in Example 4, addi- 60 Code Formln gallon DAT DAT DAT DAT tional fields tests were carried in the St. Louis area in July of SBK Super BK 32 3.2 60 90 SO 65 2003, in order to further evaluate the performance of various SPC Spectra conc 5 70 94 7O 80 ENF Enforcer 2.56 65 90 55 60 formulations on poison ivy, as well as all weeds present. (See BBG Brush-B-Gon 4 60 85 55 60 Tables 1.1, 1.2 and 3 for additional details on product formu- F3M 18 + 2 6 90 1OO 90 96 65 FSM 1 + 0.1 RTU 85 100 85 96 lations.) The results of these tests are presented in Table 5, RUP Rup RTU RTU 8O 99 80 94 below. US 8,586,504 B2 55 56 TABLE 5-continued 14. The aqueous herbicidal composition as set forth in claim 1 wherein the glyphosate concentration ranges from Summary of Test Results about 100 to about 400 grams per liter a.e. and the triclopyr Poison Ivy Total weed concentration ranges from about 8 to about 20grams per liter Rate in % injury % injury 5 a.C.

Formuln ozf1 6 12 6 12 15. An aqueous herbicidal composition as set forth in claim Code Formln gallon DAT DAT DAT DAT 1 wherein triclopyr is present in its acid or salt form. 16. A method for killing or controlling the growth of RU1 27% Rup 6 90 90 8O 85 unwanted plants comprising contacting the foliage of said Brush 10 plants with a herbicidally effective amount of the herbicidal composition of claim 1. 17. An aqueous herbicidal composition useful for killing or What is claimed is: controlling the growth of unwanted plants comprising: 1. An aqueous herbicidal composition useful for killing or glyphosate, wherein the glyphosate is predominantly in the controlling the growth of unwanted plants comprising: 15 form of potassium glyphosate, monoethanolamine gly glyphosate or a salt or ester thereof; phosate, or a mixture thereof, and triclopyr or a salt or ester thereof; and, a pyridine analog selected from the group consisting of at least one surfactant; triclopyr or a herbicidal derivative thereof; wherein the glyphosate, on an acid equivalent basis, and wherein (i) the glyphosate salt is present in a concentration the triclopyr, on an acid equivalent basis, are present in a less than 180 grams acid equivalent per liter and the weight ratio of from 8:1 to about 20:1, and further glyphosate salt (acid equivalent basis) and the pyridine wherein when the glyphosate is predominantly in the analog (acid equivalent basis) are present in a weight form of a salt, said salt is selected from the group con ratio of at least 1:1, glyphosate being in excess; (ii) the sisting of a sodium salt, an ammonium salt, an alkylam 25 glyphosate salt is present in a concentration less than monium salt, a C-C alkanolammonium salt, a di-am 240 grams acid equivalent per liter and the glyphosate monium salt, an alkylamine salt, a C-C alkanolamine salt (acid equivalent basis) and the pyridine analog (acid salt, an alkylsulfonium salt, a Sulfoxonium salt, and equivalent basis) are present in a weight ratio of at least combinations thereof. 2:1; (iii) the glyphosate salt is present in a concentration 2. The aqueous herbicidal composition of claim 1 wherein 30 the glyphosate concentration ranges from about 4 grams to less than 270 grams acid equivalent per liter and the about 25 grams acid equivalent per liter. glyphosate salt (acid equivalent basis) and the pyridine 3. The aqueous herbicidal composition of claim 1 wherein analog (acid equivalent basis) are present in a weight the triclopyr concentration ranges from about 0.4 grams to ratio of at least 3:1; (iv) the glyphosate salt is present in about 6 grams acid equivalent per liter. 35 a concentration less than 288 grams acid equivalent per 4. The aqueous herbicidal composition of claim 1 wherein liter and the glyphosate salt (acid equivalent basis) and the weight ratio (a.e. basis) of glyphosate to triclopyr ranges the pyridine analog (acid equivalent basis) are present in from about 8:1 to about 15:1. a weight ratio of at least 4:1; (v) the glyphosate salt is 5. The aqueous herbicidal liquid concentrate of claim 1 present in a concentration less than 300 grams acid wherein the glyphosate concentration ranges from at least 40 equivalent per liter and the glyphosate salt (acid equiva about 100 grams to about 400 grams acid equivalent per liter. lent basis) and the pyridine analog (acid equivalent 6. The aqueous herbicidal liquid concentrate of claim 1 basis) are presentina weight ratio of at least 5:1; (vi) the wherein the triclopyr concentration ranges from at least about glyphosate salt is present in a concentration less than 8 to about 20 grams acid equivalent per liter. 308 grams acid equivalent per liter and the glyphosate 7. The aqueous herbicidal liquid concentrate of claim 1 45 salt (acid equivalent basis) and the pyridine analog (acid wherein the glyphosate concentration ranges from at least equivalent basis) are present in a weight ratio of at least about 75 grams to about 160 grams acid equivalent per liter. 6:1, (vii) the glyphosate salt is present in a concentration 8. The aqueous herbicidal composition of claim 1 wherein less than 315 grams acid equivalent per liter and the the triclopyr concentration ranges from about 0.4 grams to glyphosate salt (acid equivalent basis) and the pyridine about 3 grams acid equivalent per liter. 50 analog (acid equivalent basis) are present in a weight 9. The aqueous herbicidal composition of claim 1 wherein ratio of at least 7:1; (viii) the glyphosate salt is present in the Surfactant concentration is not greater than 9.3 grams per a concentration less than 320 grams acid equivalent per liter. liter and the glyphosate salt (acid equivalent basis) and 10. The aqueous herbicidal composition of claim 1 wherein the pyridine analog (acid equivalent basis) are present in the Surfactant concentration is not greater than 6.6 grams per 55 a weight ratio of at least 8:1; (ix) the glyphosate salt is liter. present in a concentration less than 324 grams acid 11. The aqueous herbicidal composition of claim 1 wherein equivalent per liter and the glyphosate salt (acid equiva the Surfactant concentration is not greater than 3.9 grams per lent basis) and the pyridine analog (acid equivalent liter. basis) are present in a weight ratio of at least 9:1; or (X) 12. The aqueous herbicidal composition as set forth in 60 the glyphosate salt is present in a concentration less than claim 1 wherein the glyphosate concentration ranges from 326 grams acid equivalent per liter and the glyphosate about 4 to about 25 grams per liter a.e. and the triclopyr salt (acid equivalent basis) and the pyridine analog (acid concentration ranges from about 0.4 to about 6 grams per liter equivalent basis) are present in a weight ratio of at least a.C. 10:1. 13. The aqueous composition as set forth in claim 12 65 18. The aqueous herbicidal composition of claim 17 wherein the triclopyr concentration ranges from about 0.4 to wherein the glyphosate concentration ranges from about 4 about 3 grams per litera.e. grams to about 25 grams acid equivalent per liter. US 8,586,504 B2 57 58 19. The aqueous herbicidal composition of claim 17 wherein R' is hydrocarbylor substituted hydrocarbyl having wherein the pyridine analog concentration ranges from about from 1 to about 30 carbonatoms, R in each of thex (RO)and 0.8 grams to about 2 grams acid equivalent per liter. y (RO) groups is independently C-C alkylene, R is hydro 20. The aqueous herbicidal composition of claim 17 gen, or a linear or branched alkyl group having from 1 to wherein the weight ratio (a.e. basis) of glyphosate to pyridine about 4 carbon atoms, R is hydrogen or hydrocarbyl or analog is at least about 11:1. substituted hydrocarbyl having from 1 to about 30 carbon 21. The aqueous herbicidal composition of claim 17 atoms, Xandy are independently an average number from 1 to wherein the weight ratio (a.e. basis) of glyphosate to pyridine about 40, and X- is an agriculturally acceptable anion; analog is at least about 15:1. (d) a monoalkoxylated quaternary ammonium salt having 22. The aqueous herbicidal composition of claim 17 further 10 the formula: comprising a Surfactant. 23. The aqueous herbicidal composition of claim 17 com prising between about 4 and about 25 grams per liter glypho (4) sate a.e. and between about 0.4 and about 6 grams per liter R5 triclopyria.e. 15 24. The aqueous herbicidal composition of claim 17 com prising between about 100 and about 400 grams per liter R4 glyphosate a.e. and between about 8 and about 20grams per liter triclopyria.e. wherein R' and Rare independently hydrogen or hydrocar 25. A method for killing or controlling the growth of byl or substituted hydrocarbyl having from 1 to about 30 unwanted plants comprising contacting the foliage of said carbon atoms, R is hydrocarbyl or substituted hydrocarbyl plants with a herbicidally effective amount of the herbicidal having from 1 to about 30 carbon atoms, R in each of the X composition of claim 17. (RO) groups is independently C-C alkylene, R is hydro 26. The aqueous herbicidal liquid concentrate of claim 1 or gen, or a linear or branched alkyl group having from 1 to claim 22 wherein said Surfactant is selected from the group 25 about 30 carbon atoms, X is an average number from 1 to consisting of: about 60, and X- is an agriculturally acceptable anion; (a) a secondary or tertiary amine having the formula: (e)a quaternary ammonium salt having the formula:

30 (1) (5)

35 wherein R' and Rare hydrocarbyl having from 1 to about 30 carbonatoms, andR is hydrogenorhydrocarbyl having from wherein R', RandR are independently hydrogen or hydro 1 to about 30 carbon atoms; carbyl or substituted hydrocarbyl having from 1 to about 30 (b) a monoalkoxylated amine having the formula: carbon atoms, R is hydrocarbyl or substituted hydrocarbyl 40 having from 1 to about 30 carbon atoms, and X- is an agriculturally acceptable anion; (2) (f) an ether amines having the formula: (RO), R R-N V 45 (6) R4 wherein R' and Rare independently hydrocarbyl or substi tuted hydrocarbyl groups having from 1 to about 30 carbon atoms or RSR, R in each of the X (RO) groups is 50 independently C-C alkylene, R is hydrogen, or a linear or wherein R' is hydrocarbyl or substituted hydrocarbyl having branched alkyl group having from 1 to about 4 carbon atoms, from 1 to about 30 carbon atoms; R is hydrocarbylene or R is a linear or branched alkyl group having from about 6 to substituted hydrocarbylene having from 2 to about 30 carbon about 30 carbon atoms, R is a hydrocarbyl or substituted atoms; RandR are independently hydrogen, hydrocarbylor 55 substituted hydrocarbyl having from 1 to about 30 carbon hydrocarbyl group having from 4 to about 15 carbon atoms atoms, or —(RO),R, R in each of the x(R—O) groups is and X is an average number from 1 to about 60; independently C-C alkylene, R is hydrogen, or a linear or (c) a dialkoxylated quaternary ammonium salt having the branched alkyl group having from 1 to about 4 carbon atoms, formula: and X is an average number from 1 to about 50: 60 (g) a diamine having the formula: (3) (RO), R (7)

65 R-X-R-i-ro-R-N-R US 8,586,504 B2 59 60 wherein R', R, R and R are independently hydrogen, average number from 1 to about 50; R and R'' are each hydrocarbyl or substituted hydrocarbyl having from 1 to independently hydrocarbylene or substituted hydrocarbylene about 30 carbon atoms, or —(RO), R7: Rand Rare inde having from 1 to about 6 carbon atoms; R is hydrocarbylene pendently hydrocarbylene or substituted hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 car having from 2 to about 30 carbon atoms, R in each of the X bon atoms; R' is hydrogen or hydrocarbyl or substituted (RO) and y (RO) groups is independently C-C alkylene, hydrocarbyl having from 1 to about 30 carbon atoms; m and R’ is hydrogen, or a linear or branched alkyl group having s are each independently 0 or 1; R is hydrocarbylene or from 1 to about 30 carbonatoms, X is an average number from substituted hydrocarbylene having from 2 to about 30 carbon 1 to about 30, X is —O , N(R) , —C(O) , —C(O) atoms, –C(=NR')—, —C(S)-, or—C(O)—; q is an inte O –OC(O) - N(R)C(O) = C(O)N(R) - S -, 10 ger from 0 to 5; and R is hydrogen or hydrocarbyl or substi —SO—, or—SO , y is 0 or an average number from 1 to tuted hydrocarbyl having from 1 to about 30 carbon atoms: about 30, n and Zare independently 0 or 1, and R is hydrogen (k) a quaternary ammonium, Sulfonium and Sulfoxonium or hydrocarbyl or substituted hydrocarbyl: salt having the formula: (h) an amine oxide having the formula: 15 (12) (8) O R-x-R-Ro-R-N-- A R2 R9 O (13) wherein R, R and Rare independently hydrogen, hydro R10 R5 R7 carbyl or substituted hydrocarbyl, —(RO),R, or —R (OR), OR: R in each of the X (RO) groups is indepen 25 dently C-C alkylene, R is hydrogen, or a linear or branched A R--R)-(Ro-R-NR,--R A alkyl group having from 1 to about 30 carbon atoms, R is R11 R9 O hydrocarbylene or substituted hydrocarbylene having from 2 (14) to about 6 carbon atoms, X is an average number from 1 to R10 R5 R7 about 50, and the total number of carbonatoms in R, R and 30 R is at least 8: A R-s-R)-(Ro-R-N--R A (i) a dialkoxylated amine having the formula: R9 O (15) 35 O R5 R7 (9) (RO), R R-N A R-s-R-Ro-R-N-- A Yeo( yR3 40 wherein R', R. R. R. RandR'' are independently hydro wherein R' is a hydrocarbyl or substituted hydrocarbyl hav gen, hydrocarbyl or substituted hydrocarbyl having from 1 to ing from about 6 to about 30 carbon atoms, or—RSR, R' about 30 carbon atoms, or -(R') (RO),R': X is -O-, and R in each of the X (RO) and the y (RO) groups is OC(O) , N(R')C(O) C(O)N(R') C(O) independently C-C alkylene, R is hydrogen, or a linear or 45 O—, or—S : R in each of the n (RO) groups and V (RO) branched alkyl group having from 1 to about 4 carbon atoms, groups is independently C-C alkylene; R' is hydrogen, or R is a linear or branched alkyl group having from about 4 to a linear or branched alkyl group having from 1 to about 30 about 15 carbon atoms, and X and y are independently an carbonatoms; n is an average number from 1 to about 60; V is average number from 1 to about 40; an average number from 1 to about 50; R and R' are each () an aminated alkoxylated alcohol having the structure: 50 independently hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms; m and S are each independently 0 or 1; R is hydrocarbylene or substituted (10) hydrocarbylene having from 2 to about 6 carbonatoms; R is hydrocarbylene or substituted hydrocarbylene having from 2 M to about 30 carbon atoms, —C(=NR') , —C(S) , or 55 —C(O) ; R'' is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, q is an integer from 0 to 5; R is hydrogen or hydrocarbyl or substi wherein R. R. R. and Rare each independently hydrogen, tuted hydrocarbyl having from 1 to about 30 carbon atoms: hydrocarbyl or substituted hydrocarbyl having from 1 to 60 and each A is an agriculturally acceptable anion; about 30 carbon atoms, or —(R'),(RO),R': X is —O , (1) a diamine or diammonium salt having the formula: –OC(O) , —C(O)C-, - N(R')C(O)—, C(O)N (R') ,—S , SO = SO or N(R) : R in each of the n (RO) groups and the V (RO) groups is indepen dently C-C alkylene; R' is hydrogen, or a linear or 65 branched alkyl group having from 1 to about 30 carbon R6 Rs O atoms; n is an average number from 1 to about 60; V is an US 8,586,504 B2 61 62 -continued wherein R' and Rare independently hydrogen, or a linear or (17) branched alkyl group having from 1 to about 30 carbon atoms R8 and at least one of R' and R is an alkyl group, R in each of R-(R-O--N-R-N-(R-O--R 2X the X (RO) groups is independently C-C alkylene, R is hydrogen, or a linear or branched alkyl group having from 1 R6 Rs to about 4 carbonatoms, and X is an average number from 1 to about 60: wherein R', R. R. R. R7 and Rare independently hydro (o) an alkyl alkoxylated phosphate having the formula: gen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R in each of the m (RO) and in 10 (RO) groups and Rare independently C-C alkylene, R is (20) hydrocarbylene or substituted hydrocarbylene having from R-O-(RO) O about 2 to about 6 carbon atoms or —(RO).R. , m and in Drz are individually an average number from 0 to about 50, and p R3-O-(R2O). O H. is an average number from 0 to about 60: 15 (m) an alkoxylated alcohol having the formula: wherein R' and R are independently a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, RO (RO), R (18) aryl, or aralkyl group having from about 4 to about 30 carbon wherein R' is hydrocarbyl or substituted hydrocarbyl having atoms; R in each of the m (RO) and the n (RO) groups is from 1 to about 30 carbon atoms, R in each of the X (RO) independently C-C alkylene; and mand nare independently groups is independently C-C alkylene, R is hydrogen, or a from 1 to about 30; linear or branched alkyl group having from 1 to about 4 (p) an alkyl alkoxylated phosphate having the formula: carbonatoms, and X is an average number from 1 to about 60; (n) an alkoxylated dialkylphenol having the formula: 25 (21) R'-O-(R1- n- (P2 One (19) Hi O1 No

30 wherein R' is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 30 carbonatoms; R in each of the m (RO) groups is independently C-C alkylene; and m is from 1 to about 30: (OR2), R3 35 and mixtures or combinations thereof.

k k k k k