NZ584359A - Composisiton containing glufosinate and one of acifluorfen, oxyfluorfen and fomesafen - Google Patents

Abstract

Disclosed is a non-selective, synergistic herbicidal composition comprising as active ingredients: (A) selected from glufosinate, glufosinate-P, and salts thereof, and (B) oxyfluorfen, the composition being characterised in that active ingredients (A) and (B) are present in synergistically effective ratios ranging from about 20: 1 to about 1 :20 and whereby, the composition is applied at a rate ranging from about 200 gai/ha to about 2,500 gai/ha, based on the combined rate of active ingredients (A) and (B). The formulation can be solid or liquid. Also disclosed is the method of non-selectively controlling weeds which comprises applying to the plants or parts of plants, plant seeds or to soil a composition comprising (A) and (B) and applied at a rate ranging from about 200 gai/ha to about 2,500 gai/ha.

Description

New Zealand Paient Spedficaiion for Paient Number 584359 Patents Form # 5 NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION AFTER PROVISIONAL NO.: 584359 PRIORITY DATE : 31 March 2010 TITLE : Synergistic Herbicidal Mixtures We, ZELAM LIMITED Address: 5 Hudson Road, RD3, New Plymouth, New Zealand, 4373 Nationality: A body corporate organized and existing under the laws of New Zealand do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: 401639NZ_Cap_20110304_1003_EMM.doc FEE CODE 1050 RECEIVED at IPONZ on 9 March 2011 SYNERGISTIC HERBICIDAL COMPOSITION BACKGROUND This invention relates to a herbicidal composition and more particularly, but not exclusively it relates to a non-selective, synergistic herbicidal composition, to its method of preparation, and to its method of use.

Non-selective herbicides such as glufosinate, glyphosate and paraquat are commonly used in agriculture and horticulture for a number of purposes including post harvest cleanup, total knockdown of existing herbage prior to cultivation and/or resowing, weed control in non-farmed areas and fallow land, weed control in the presence of crops, especially in orchards and vineyards, use as desiccants or for primocane control, and weed control in conjunction with other herbicides as part of herbicide resistance strategies.

Paraquat controls a broad range of weeds but is dangerous to users and fatal if swallowed or absorbed through the skin, whereas glufosinate and glyphosate are both very safe for users. Glyphosate is the most widely used non-selective herbicide, it is relatively cheap and controls a broad range of weeds. Glyphosate is fully systemic, being translocated to all parts of the plant following foliar uptake. This has certain disadvantages in that use of glyphosate to control weeds in horticulture, for example, is restricted to periods of crop dormancy and/or it must be applied with great care to avoid crop contact. Glufosinate, on the other hand, is only partially systemic in its action with limited movement following uptake by foliage and green stems, there is no root uptake and no residual activity in the soil. This presents an advantage over glyphosate and accordingly glufosinate is widely used to control weeds under fruit trees and grape vines, for example, and may be applied safely after bud burst.

Whereas application rates in the range 600 to 1,000 grams of active ingredient per hectare (gai/ha) of glufosinate-ammonium are sufficient to control a range of common weeds such as Poa annua, chickweed and willow weed, considerably higher rates (1,000 - 2,000 gai/ha) are required for other 2 RECEIVED at IPONZ on 9 March 2011 common weeds such as clover, field pansy, fleabane, mallows, paspalum, tall fescue, willow herb and yarrow, and still higher rates (>2,000 gai/ha) are required to control other weeds such as plantains, rape, sedges and bracken. Early symptoms of herbicidal activity (brownout) are useful in revealing areas needing to be re-sprayed, but can take one to two weeks to appear when glufosinate is used. Furthermore, glufosinate has negligible residual activity, often necessitating repeat applications. It is desirable to increase the number of weeds controlled by glufosinate, to lower application rates, to increase the rapidity of brownout, and in certain circumstances to increase the residual activity of this herbicide.

All references, including any patents or patent applications cited in this specification are hereby incorporated by reference. The applicant makes no admission that any reference constitutes prior art - they are merely assertions by their authors and the applicant reserves the right to contest the accuracy, pertinence and domain of the cited documents. None of the documents or references constitutes an admission that they form part of the common general knowledge in NZ or in any other country SUMMARY It is an object of the invention to provide an improved composition and/or preparative method thereof and/or use thereof which will obviate or minimize one or more of the previously mentioned disadvantages, or which will at least provide the public with a useful choice.

Surprisingly, we have found that a non-selective, herbicidal composition comprising as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof, yield synergistic herbicidal activity against a range of weeds. The effective dose required can be lowered as a result of the synergy making the resulting products and crop production systems more economical, and minimising or eliminating one or more of the previously mentioned problems.

Surprisingly, we have found that a composition comprising as active ingredients: (A) selected from glufosinate, glufosinate-P or salts thereof and (B) at least one nitrophenyl ether herbicide or esters 3 RECEIVED at IPONZ on 9 March 2011 or salts thereof offer considerably better herbicidal control when administered simultaneously or sequentially. That is, when the herbicidal composition is administered as a joint of active ingredients (A) and (B); or as successive applications of (A) and (B) it allows for significantly improved herbicidal control than is possible with the administration of the individual compounds alone In one broad aspect this invention provides a non-selective, synergistic herbicidal composition comprising as active ingredients: (A) selected from glufosinate, glufosinate-P, and salts thereof, and (B) at least one nitrophenyl ether herbicide selected from acifluorfen, fluoroglycofen, fomesafen, lactofen, oxyfluorfen, and esters or salts thereof, characterised in that active ingredients (A) and (B) are present in synergistically effective ratios ranging from about 100:1 to 1:100 and whereby, in use, the composition is applied at a rate ranging from about 200 gai/ha to about 2,500 gai/ha, based on the combined rate of active ingredients (A) and (B).

Preferably, the ratio of (A):(B) is 10:1 to 1:10 Preferably, the ratio of (A):(B) is 5:1 to 1:5 Preferably, the composition is applied at a rate ranging from about 400 gai/ha to about 2,000 gai/ha, based on the combined rate of active ingredients (A) and (B).

Preferably, the composition is applied at a rate ranging from about 600 gai/ha to about 1,000 gai/ha, based on the combined rate of active ingredients (A) and (B).

In a further broad aspect this invention provides methods of formulating the non-selective, synergistic herbicidal compositions of the invention. 4 RECEIVED at IPONZ on 9 March 2011 In a further broad aspect this invention provides a method of controlling weeds, which comprises applying to plants, parts of plants, plant seeds, or to soil, herbicidal synergistically effective amounts of herbicidal compositions comprising as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof.

RECEIVED at IPONZ on 9 March 2011 DETAILED DESCRIPTION This invention relates generally to combinations of herbicidal active ingredients and more particularly to synergistic compositions of herbicidal active ingredients providing for more effective and broader control of weed species and/or an increase in crop safety and/or an increase in residual herbicidal activity.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as would be readily understood by one of ordinary skill in the art to which this invention belongs.

The term "herbicidal" encompasses all plant growth controlling or modifying effects including, but not limited, to killing, halting, stalling, retarding, stunting, dwarfing, leaf burn, albinism, suppression, distortion, twisting, abnormal irregular growth, inhibition of growth, inhibition of germination, disruption of flowering, and the like. Moreover the term "herbicidal" includes partial, intermediary, transitional or reversible effects including, but not limited to, discolouration, yellowing, browning, whitening, bleaching, chlorosis, various other phytotoxic effects, and the like. The term "herbicidally effective amount" indicates the quantity or application rate of a herbicidal composition which is capable of producing any one or more such plant growth controlling or modifying effects. The terms "plant" or "plants" refer to whole plants and/or plant parts including, but not limited to, seeds and other propagules, seedlings, roots, tubers, corms, offsets, runners, stems, stalks, buds, foliage, flowers and fruits.

A "non-selective herbicide" is used to kill all plants (crops plus weeds) in a desired target zone, as opposed to a selective herbicide, which is sprayed over a crop to kill weeds without injury to the crop. In other words a non-selective herbicide doesn't discriminate between target and non-target pests.

The term "synergistic" refers to a particular effect and may be calculated as defined by R. S. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", 1967, Weeds 15, 20-22). Colby's publication discloses the formula: E = X + Y - (XY)/100, in which, 6 RECEIVED at IPONZ on 9 March 2011 X represents the percent inhibition of growth by herbicide A at jc grams of active ingredient per hectare (gai/ha), Y represents the percent inhibition of growth by herbicide B at y gai/ha, and E represents the "Expected" percent inhibition of growth by herbicides A + B in combination atx+y gai/ha, respectively.

When the observed percent inhibition of growth by herbicides A + B is greater than "Expected", the combination is synergistic. If the observed inhibition is less than "Expected", the combination is antagonistic, and when observed and "Expected" inhibitions are equal, the combination is additive. Colby also presents alternative methods of calculation for original data expressed as percent-of-control values and for three-way synergistic interactions.

Surprisingly, we have found that herbicidal compositions comprising as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof, yield synergistic herbicidal activity against a range of weeds, i.e., the inhibitory effects on weed growth by the combinations of active ingredients is unexpectedly greater than the "Expected" effects calculated using the Colby formula based on the effects of individual active ingredients. The effective application rates required can be lowered as a result of the synergy making the resulting products and crop production systems more economical, and minimising or eliminating one or more of the previously mentioned problems.

If the active ingredients in the synergistic composition according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active ingredients in the synergistic composition can be varied within a relatively wide range. The ratios of active ingredients (A) to (B) indicated in this disclosure do not in any way limit the scope of this invention, but rather are mentioned as a guide, a person of ordinary skill in the art being entirely capable of carrying out complementary experiments in order to find other values of the ratios of active ingredients which produce a synergistic effect.

The disclosed herbicidal composition may comprise as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters 7 RECEIVED at IPONZ on 9 March 2011 or salts thereof, the active ingredients (A) and (B) being in ratios producing a synergistic herbicidal effect.

Active ingredient (A) comprises glufosinate in one or more of several forms including: glufosinate ((2i?5)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid), the unresolved isomer, glufosinate-P ((25)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid), the (S)-isomer, and salts thereof.

The invention includes all herbicidally active forms of glufosinate and glufosinate-P including acids, salts and partial salts. In addition to the acid forms of glufosinate and glufosinate-P these compounds may be used as salts together with agriculturally suitable inorganic and/or inorganic counterions. Examples of suitable counterions may include but are not limited to alkali metal ions, alkaline earth metal ions, ammonium ions, quaternary ammonium ions, organic amines, the conjugate bases of organic and inorganic acids. Ammonium or sodium salts are most suitable, the most common of which are identified as glufosinate-ammonium, glufosinate-P-ammonium and glufosinate-P-sodium.

Examples of suitable nitrophenyl ether herbicides may include, but are not limited to: acifluorfen (5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2-nitrobenzoic acid), fluoroglycofen (0-[5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2-nitrobenzoyl]glycolic acid), fomesafen (5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-iV-mesyl-2-nitrobenzarnide), lactofen (ethyl 0-[5-(2-chloro-a,a,a-trifluoro-p-tolyloxy)-2-nitrobenzoyl]-DL-lactate). oxyfluorfen (2-chloro-a,a,a-trifluoro-p-tolyl 3-ethoxy-4-nitrophenyl ether), and esters and salts thereof.

The invention includes all herbicidally active forms of nitrophenyl ether herbicides including acids, esters, salts and partial salts. Acifluorfen and fluoroglycofen contain esterifiable carboxylic acid 8 RECEIVED at IPONZ on 9 March 2011 groups which may be reacted with a range of alcohols. Lactofen is the ethyl lactate ester of acifluorfen, fluoroglycofen is the glycolic acid (hydroxyacetic acid) ester of acifluorfen, and fluoroglycofen-ethyl is the ethyl ester of fluoroglycofen. Salts and partial salts may be formed by virtue of the carboxylic acid moieties of acifluorfen and fluoroglycofen, and the amide group of fomesafen. Examples of suitable counterions may include but are not limited to alkali metal ions, alkaline earth metal ions, ammonium ions, quaternary ammonium ions, organic amines, and the conjugate bases of organic and inorganic acids.

Preferably active ingredient (B) is one or more nitrophenyl ether herbicides selected from the group consisting of acifluorfen, fluoroglycofen, fomesafen, lactofen, oxyfluorfen, and esters or salts thereof. More preferably active ingredient (B) is selected from the group comprising acifluorfen, fomesafen, oxyfluorfen, and salts or esters thereof. Still more preferably active ingredient (B) is oxyfluorfen.

The chosen forms of active ingredient (A) and (B) may be based on their respective solubilities in different solvents and the type of formulation desired, for example, and taking into account other properties such as active ingredient volatility and consequent effects on herbicidal activity or unwanted crop effects.

According to the invention, synergistic combinations of active ingredients (A) and (B) may be found when the relative amounts of active ingredients (A) and (B) are present within the range, expressed as aratio (A):(B), from about 1:0.001 to about 1:1,000 parts by weight. Suitably active ingredients (A) and (B) are present in a ratio (A):(B) from about 1:0.01 to about 1:100 parts by weight. More suitably active ingredients (A) and (B) are present in a ratio (A):(B) from about 1:0.02 to about 1:50 parts by weight. Still more suitably active ingredients (A) and (B) are present in a ratio (A):(B) from about 1:0.05 to about 1:20 parts by weight.

The composition may comprise 0.1% to 50% active ingredient (A) and 0.1% to 50% active ingredient (B) on a weight/weight basis or a weight/volume basis. The percentages of active ingredients in the composition will depend mainly on the formulation type and intended method of application. 9 RECEIVED at IPONZ on 9 March 2011 Suitable formulation types and methods are described, for example, in "Chemistry and Technology of Agrochemical Formulations", 1998, D. A. Knowles (editor), Kluwer Academic Publishers, "Pesticide Formulation and Adjuvant Technology", 1966, C. L. Foy (editor), CRC Press, and "Formulation Technology: Emulsions, Suspensions, Solid Forms", 2001, H. Mollet and A. Grubenmann, Wiley-VCH. Suitable formulation types for the herbicidal composition include, but are not limited to, a granule, a powder, a concentrate, a gel, a solution, an emulsion, a dispersion, a suspension, or a controlled release form including a microcapsule.

Advantageously the formulation is a liquid or a granule thus minimising exposure of users to the hazards of powders and dusts. More suitable formulation types are a water dispersible granule, a concentrate, a solution, an emulsion, an oil dispersion, a paste, a suspension concentrate, or a microcapsule suspension, or a composition thereof.

In addition to active ingredients (A) and (B), the herbicidal composition may contain 0.1% to 99% of customary formulation additives. Customary formulation additives and their functions are described in the previously mentioned publications. Such additives may include water, agriculturally suitable surfactants, dispersants, emulsifiers, penetrants, spreaders, wetting agents, soaps, carriers, oils, solvents, diluents, inert components, conditioning agents, colloids, suspending agents, thickeners, thixotropic agents, polymers, emollients, acids, bases, salts, organic and inorganic solid matrices of various kinds, preservatives, anti-foam agents, anti-freeze agents, anti-caking agents, lubricants, stickers, binders, glues, resins, complexing agents, chelating agents, crystallization inhibitors, dyes, activators, synergists, safeners, UV protectants, fertilizers, micronutrients, and the like.

Certain additives are known to increase the herbicidal efficacy of the active ingredients comprising the composition of this invention, for example a crop oil concentrate containing appropriate surfactants. In some cases the additives may be included in the formulation but in other cases may be incompatible and therefore must be introduced as a "tank mixture". Furthermore, herbicidal efficacy may be augmented by admixture of the composition with other, non-herbicidal pesticide formulations that contain oils, organic solvents and the like, for example an insecticide formulated as an emulsifiable concentrate. Potential adverse impacts on crop tolerance must be considered RECEIVED at IPONZ on 9 March 2011 when preparing such mixtures in accordance with good agricultural practice and label recommendations.

Enhanced crop protection may be achieved without compromising herbicidal activity by microencapsulation of active ingredient (B), which may be readily achieved with the water-insoluble nitrophenyl ether herbicides of the composition.

Compositions are formulated using known methods by dissolving, dispersing, finely dividing, slurrying, emulsifying, homogenizing, stirring, high-shear mixing, comminuting, milling, stabilising, etc, the active ingredients, and by admixing with appropriate quantities of the one or more previously mentioned customary formulation additives to form the composition of the invention. Further details of suitable methods of manufacture of the composition are provided in the examples.

The invention provides a method of controlling weeds, which comprises applying to plants, parts of plants, plant seeds or to soil, herbicidally effective amounts of synergistic herbicidal compositions comprising as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof.

The method is applicable to any cropping situation including vegetation control in non-farmed areas and fallow land, knockdown of existing herbage prior to cultivation and resowing, certain pre-emergence situations, post-emergence weed control such as inter-row spraying of annual crops, and control of established weeds within established crops and trees, including plantation forestry for production of timber or lumber, lignocellulosic biomass, oil seeds, rubber, cotton, coffee, sugar cane, sisal, and the like. The invention is particularly suitable for weed control in orchards and vineyards where it may be applied safely after budburst.

The composition may be applied at any stage of the crop cycle. The composition may be applied at any time for vegetation control in non-farmed areas and fallow land or for knockdown of existing herbage prior to cultivation and/or resowing. The composition may be applied at any time for weed control among established crop species such as in a plantation forest or among trees and vines in 11 RECEIVED at IPONZ on 9 March 2011 orchards and vineyards, although extra care may be necessary to avoid foliar or stem contact during active crop growth periods.

In general the composition may be diluted into a carrier and applied by conventional means to soil, plants and parts thereof. Water is the carrier of choice and the formulation may be mixed into water and applied by spraying, sprinkling or wicking. Directed application is advisable in orchards and vineyards.

Other biocidal active ingredients may be combined with the herbicidal composition of the invention, and may include other herbicides, fungicides, bactericides, insecticides, nematicides, and the like. These active ingredients may be added as a "tank mixture".

Active ingredients (A) and (B) of the composition may be applied sequentially or, preferably, simultaneously. The active ingredients together with other additives are advantageously pre-formulated as a single composition. It should be emphasised that active ingredients (A) and (B) of the composition may also be formulated separately and "tank mixed" prior to application. Various combinations of separately formulated active ingredients and other customary formulation additives, and the mixing thereof, can be envisaged in the tank mixing scenario. A common occurrence may be the addition of one or more surfactants during tank mixing. Active ingredients (A) and (B) may be applied sequentially, in any order and in any effective timescale, suitably within a one week period, more suitably within a 24 hour period, and, preferably, within one hour.

The use rate for the composition is dependent on the timing and method of application, the range of weed species to be controlled, the degree of control required, as well as the herbicide tolerance of the crop. The composition can be applied at a rate ranging from about 1 gram active ingredient per hectare (gai/ha) to about 2,500 gai/ha, based on the combined rate of active ingredients (A) and (B). Suitable use rates for active ingredient (A) range from about 1 gai/ha to about 2,000 gai/ha. Preferred use rates for (A) range from about 10 gai/ha to about 1,600 gai/ha. More preferred rates for (A) range from about 200 gai/ha to about 1,200 gai/ha. Still more preferred rates for (A) range from about 400 gai/ha to about 1,200 gai/ha. Suitable use rates for active ingredient (B) range from about 1 gai/ha to about 500 gai/ha. Preferred use rates for (B) range from about 1 gai/ha to about 12 RECEIVED at IPONZ on 9 March 2011 250 gai/ha. More preferred use rates for (B) range from about 20 gai/ha to about 200 gai/ha. Still more preferred use rates for (B) range from about 40 gai/ha to about 120 gai/ha. A person of ordinary skill in the art will acknowledge the value of product label claims and directions for use in determining suitable applications and use rates for the compositions of this invention.

The non-selective, synergistic herbicidal composition comprising active ingredients (A) and (B) may be used to control many monocotyledonous and dicotyledonous plants, including annual and perennial grasses, a large number ofbroadleaf weeds, clovers, certain brush weeds and sedges. 13 RECEIVED at IPONZ on 9 March 2011 The following examples and the particular proportions set forth are intended to be illustrative only and are thus non-limiting.

EXAMPLE 1. Glufosinate ammonium soluble concentrate 200 gai/Litre containing oxyfluorfen suspension concentrate 20 gai/Litre.

Ingredient Grams/litre Oxyfluorfen SC Water #1 11.9 Veegum 8% (w/v) #1 4.9 Gensil 2000 0.01 Reax 825E 1.0 Soprophor FL 1.8 Surfynol 104 0.01 Oxyfluorfen .0 Methylchloroisothiazolinone 0.01 Glufosinate SL Water #2 611.4 Glufosinate ammonium 200 Monoethanolamine 7.2 Veegum 8% (w/v) #2 100 Xanthum gum 1.0 Propylene glycol .7 NaC12/C14 Pareth sulphate 100 Prepare the oxyfluorfen SC and glufosinate SL separately before combining. Oxyfluorfen SC: Mix the reagents in the order provided above with good stirring at each addition and ensuring that oxyfluorfen is added in small quantities and completely dispersed prior to the next addition. Bead 14 RECEIVED at IPONZ on 9 March 2011 mill the oxyfluorfen slurry to give a final particle size <5 |im. Glufosinate SL: Dissolve the glufosinate ammonium into water #2 then add the remaining components in the order shown. Stir the two parts together, preferably using a high shear blender in order to complete formulation.

EXAMPLE 2. Glufosinate soluble concentrate 200 gai/Litre containing oxyfluorfen capsule suspension 20 gai/Litre.

Prepare oxyfluorfen as a capsule suspension by dissolving 20 grams of oxyfluorfen in 46.7 grams Aromatic 150 and adding 2.4 grams of pMDI. Emulsify the resulting solution in an aqueous solution of 5% w/v PVA at a temperature of 25°C using a Silverson high shear mixer and subsequently cure with a 10% aqueous solution of diethylenetriamine. The resulting capsules, sized 1 to 5 (am, are diluted to approximately 110 mL, then combined with the glufosinate SL prepared as in described Example 1 except that the volume of Water #2 is 456 mL.

RECEIVED at IPONZ on 9 March 2011 EXAMPLE 3. Glufosinate ammonium soluble concentrate 200 gai/Litre containing fomesafen suspension concentrate 30 gai/Litre.

Ingredient Grams/litre Fomesafen SC Water #1 17.9 Veegum 8% (w/v) #1 7.4 Gensil 2000 0.02 Reax 825E 1.5 Soprophor FL 2.7 Surfynol 104 0.02 Fomesafen Methylchloroisothiazolinone 0.02 Glufosinate SL Water #2 601.4 Glufosinate ammonium 200 Monoethanolamine 7.2 Veegum 8% (w/v) #2 100 Xanthum gum 1.0 Propylene glycol .7 NaC12/C14 Pareth sulphate 100 Prepare the formulation as described in Example 1. 16 RECEIVED at IPONZ on 9 March 2011 EXAMPLE 4. Glufosinate ammonium 200 gai/Litre, acifluorfen sodium 50 gai/Litre soluble concentrate.

Ingredient Grams/litre Water 692.5 Triethanolamine .0 Glufosinate ammonium 200.0 Acifluorfen sodium 50.0 Na C12/C14 Pareth sulphate 100.0 Add the glufosinate ammonium and acifluorfen sodium to the water, stir to dissolve, then add the triethanolamine to raise the pH to greater 7. Add the Na C12/C14 pareth sulfate and stir until dispersed.

EXAMPLE 5. Glufosinate ammonium 200 gai/Litre fomesafen 20 gai/Litre oil dispersion.

Ingredient Grams/litre Paraffmic Spray Oil 450 Claytone HY 140 PEG-4.5 Oleate 50 PEG-3 Laurate 80 Fomesafen sodium Glufosinate ammonium 200 Silwet L-77 100 Disperse the oleophilic clay Claytone HY in the paraffmic oil with a high shear mixer. Then add the emulsifiers PEG-4.5 Oleate and PEG-3 Laurate. Blend in fomesafen sodium and glufosinate ammonium and bead mill the mixture to a particle size less than 10 microns. Finally add the organosilicone wetter Silwet L-77. 17 RECEIVED at IPONZ on 9 March 2011 EXAMPLE 6. Glufosinate ammonium 200 gai/Litre bifenox 50 gai/Litre oil dispersion.

Ingredient Grams/litre Bifenox 50 Methyl oleate 460 Solvesso 150 50 Tensiofix 869 140 Tensiofix NTM 150 Glufosinate ammonium 200 Dissolve bifenox in the solvents Methyl oleate and Solvesso 150. Disperse the oleophilic clay Tensiofix 869 in the solvent mixture with a high shear mixer. Then add the emulsifier Tensiofix NTM. Blend in glufosinate ammonium and bead mill the mixture to a particle size less than 10 microns.

EXAMPLE 7. Glufosinate ammonium 660 gai/Litre oxyfluorfen 60 gai/Litre water dispersible granule.

Ingredient Grams/litre Glufosinate ammonium 660 Oxyflourfen 60 Sodium polynaphthalene sulfonate 80 Sodium dioctyl sulfosuccinate Kaolin clay 190 Hammer mill the active ingredients Glufosinate ammonium and oxyfluorfen. Then combine with the rest of the inerts and mix to an extrudable dough with about 5 to 10% moisture. Dry the extrusion product in a fluid bed drier. 18 RECEIVED at IPONZ on 9 March 2011 In the following examples, the synergistic weed controlling effects of compositions containing actives (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof, are demonstrated for various weeds by comparison of observed percent control results with "Expected" percent control results based on the weed controlling effects of components (A) and (B) alone, calculated using the Colby formula: E = X + Y - (XY)/100, in which, X represents the % control by herbicide (A) at x gai/ha, Y represents the % control by herbicide (B) at y gai/ha, and E represents the "Expected" % control by herbicides (A) + (B) atx + y gai/ha, respectively.

When the observed % control by (A) + (B) is greater than "Expected" % control, the combination is synergistic.

Synergistic weed controlling effects were also assessed by examining regrowth of weeds a considerable period of time after herbicide application. In this case synergy is demonstrated by comparison of observed percent regrowth with "Expected" percent regrowth, and the Colby formula is applied as: E' = (X'Y')/100, in which, X' represents the % regrowth after treatment with herbicide (A) at x gai/ha, Y' represents the % regrowth after treatment with herbicide (B) at_y gai/ha, and E' represents the "Expected" % regrowth after treatment with herbicides (A) + (B) at x + y gai/ha, respectively.

When the observed % regrowth after treatment with (A) + (B) is less than "Expected" % regrowth, the combination is synergistic. 19 RECEIVED at IPONZ on 9 March 2011 EXAMPLE 8.

An established pasture consisting predominantly of annual ryegrass (Lolium multiflorum gaudini) and containing a large number of burning nettles (Urtica urens) was sprayed in preparation for ploughing and replanting with glufosinate (GLU), oxyfluorfen (OXY), or the two herbicides combined, then assessed for yellowing of ryegrass and brownout of burning nettle at the number of days after treatment (DAT) shown. Grasses and burning nettle are not well controlled by glufosinate alone and the unexpected synergy observed in combination with a relatively small amount of oxyfluorfen (Table 1) provides a very useful contribution to the efficacy of this active ingredient.

Table 1.

Treatment Ryegrass (% yellowing 6 DAT) Burning nettle (% brownout 10 DAT) GLU 600 gai/ha 75% 48% OXY 125 gai/ha 22% 45% GLU 600 gai/ha + OXY 125 gai/ha "Expected" 81% 71% GLU 600 gai/ha + OXY 125 gai/ha Observed 95% 81% EXAMPLE 9.

Ground cover under grape vines, containing a variety of grasses and weeds, was sprayed in early spring with glufosinate (GLU), microencapsulated oxyfluorfen (OXY Encaps), or the two herbicides combined. A synergistic effect was apparent on the major weeds scrambling speedwell (Veronicapersica), fumitory (Fumaria sp), and catchfly (Silene gallica), and on total weed control 30 DAT (Table 2). Speedwell, fumitory and catchfly are not labeled as weeds controlled by glufosinate but, unexpectedly, are well controlled when glufosinate is combined with oxyfluorfen.

RECEIVED at IPONZ on 9 March 2011 Table 2.

Treatment (% Chemical effect) Speedwell (5 DAT) Fumitory (5 DAT) Catchfly (9 DAT) Total weeds (30 DAT) GLU 600 gai/ha 93% % 70% 68% OXY Encaps 62.5 gai/ha 33% % % 3% GLU 600 gai/ha + OXY Encaps 62.5 gai/ha "Expected" 95% 36% 75% 68% GLU 600 gai/ha + OXY Encaps 62.5 gai/ha Observed 97% 72% 90% 84% EXAMPLE 10.

Ground cover under Semilon grape vines, containing a variety of grasses and weeds, was sprayed in mid summer with glufosinate (GLU), oxyfluorfen (OXY), or the two herbicides combined, then each assessed for % brownout 3 DAT or 7 DAT (Table 3). Soon after spraying synergistic affects were apparent on the major weed species present: white clover (Trifolium ripens), fathen (Chenopodium album), chickweed (Stellaria media), crabgrass (Digitaria sanguinalis), black nightshade (Solarium nigrum), portulaca (Portulaca sp.), scrambling speedwell (Veronica persica), fleabane (Conyza sp.), wireweed (Polygonum aviculare), shepherd's purse (Capsella bursa-pastoris) and willowherb (Epilobium sp.). Importantly, pronounced synergistic effects were observed by assessing % regrowth of individual weeds and total green plot area 28 DAT (Table 4). The synergy allows a considerable lowering of the high recommended glufosinate application rates for difficult to control weeds such as clover, fleabane and willowherb. Unexpectedly, fathen, portulaca, shepherd's purse and speedwell, which are not recognised as controlled by glufosinate, display the useful synergistic effects of the invention. 21 RECEIVED at IPONZ on 9 March 2011 Table 3.

Active ingredient gai/ha GLU 200 OXY 20 GLU 200 + OXY 20 GLU 400 OXY 40 GLU 400 + OXY 40 % Brownout (DAT) X Y E Obs X Y E Obs White clover (3) % 1% 36% 46% 49% 1% 50% 59% Fathen (3) % 3% 22% 50% 59% % 61% 85% Chickweed (3) % % 34% 72% 80% 46% 89% 90% Crabgrass (3) 46% 1% 47% 50% 54% 2% 55% 65% Nightshade (3) % 8% 26% % % % 41% 45% Portulaca (3) 16% % % 28% % 8% 31% 45% Speedwell (3) 9% 18% % 41% % 18% 39% 44% Fleabane (3) % 0% % 33% 24% 1% % 42% Wireweed (3) % 0% % % % 0% % 45% Shepherds purse (7) 64% 9% 67% 80% 79% 14% 82% 89% Willow herb (7) 71% 3% 72% 86% 96% 14% 97% 99% Table 4.

Active ingredient gai/ha GLU 200 OXY 20 GLU 200 + OXY 20 GLU 400 OXY 40 GLU 400 + OXY 40 % Regrowth (28 DAT) X' Y' E' Obs X' Y' E' Obs White clover 55% 100% 55% % 18% 100% 18% 3% Fathen 64% 100% 64% 18% 16% 99% 16% 1% Crabgrass 56% 99% 55% 36% % 100% % 2% Portulaca 55% 94% 52% 44% 40% 93% 37% 12% Total plot green 51% 100% 51% 33% 16% 100% 16% 2% 22 RECEIVED at IPONZ on 9 March 2011 EXAMPLE 11.

Weedy ground was sprayed in mid summer with glufosinate (GLU), oxyfluorfen (OXY), or the two herbicides combined, then each assessed 3 and 6 days after treatment. As shown in Table 5 synergistic herbicidal effects were apparent soon after spraying for the difficult to control species willow weed. The total knockdown data (whole plot 6 DAT, Table 5), which includes other weeds such as spurrey, catchfly and speedwell, also revealed synergistic interactions between glufosinate and oxyfluorfen at both ratios tested.

Table 5.

Active ingredient gai/ha GLU 100 OXY 100 GLU 100 + OXY 100 GLU 50 OXY 500 GLU 50 + OXY 500 % Chemical effect X Y E Obs X Y E Obs Willow weed (3 DAT) 3 31 33 69 0 49 49 69 Willow weed (6 DAT) 14 55 61 83 6 81 82 90 Whole plot (6 DAT) 3 31 33 55 3 61 62 68 It will be appreciated that the compositions provided are examples only and that other herbicidal compositions may be contemplated comprising as active ingredients: (A) selected from glufosinate, glufosinate-P and salts thereof and (B) at least one nitrophenyl ether herbicide or esters or salts thereof. The test results show that, by virtue of strong synergism, that the compositions according to the invention are, even at relatively low application rates, significantly more effective against brownout and regrowth than the comparative compounds.

Equivalents Clause.

The Invention may also broadly be said to consist in the parts, elements and features referred or indicated in the specification, individually or collectively, and any or all combinations of any of two or more parts, elements, members or features and where specific integers are mentioned herein which have known equivalents such equivalents are deemed to be incorporated herein as if individually set forth. 23

Claims (7)

1. RECEIVED at IPONZ on 9 March 2011 Modifications and Variations The invention has been described with particular reference to certain embodiments thereof. It will be understood that various modifications can be made to the above-mentioned embodiment without departing from the ambit of the invention. The skilled reader will also understand the concept of what is meant by purposive construction. The examples and the particular proportions set forth are intended to be illustrative only and are thus non-limiting. Throughout the description and claims of the specification the word "comprise" or variations thereof are not intended to exclude other additives, components or steps. Kit of Parts It will also be understood that where a product, method or process as herein described or claimed and that is sold incomplete, as individual components, or as a "kit of Parts", that such exploitation will fall within the ambit of the invention. 24 RECEIVED at IPONZ on 29 July 2011 CLAIMS 1 A non-selective, synergistic herbicidal composition comprising as active ingredients: (A) selected from glufosinate, glufosinate-P, and salts thereof, and (B) oxyfluorfen, the composition being characterised in that active ingredients (A) and (B) are present in synergistically effective ratios ranging from about 20:1 to about 1:20 and whereby, the composition is applied at a rate ranging from about 200 gai/ha to about 2,500 gai/ha, based on the combined rate of active ingredients (A) and (B).
2. 2 The herbicidal composition according to claim 1 wherein the weight ratio (A):(B) is from about 10:1 to about 1:10.
3. 3 The herbicidal composition according to claim 1 or claim 2 wherein the herbicidal composition is applied at a rate ranging from about 400 gai/ha to about 2,000 gai/ha.
4. 4 The herbicidal composition according to any one of claims 1 to 3 comprising 2% to 50% of active ingredient (A) and 2% to 50% of active ingredient (B) on a weight/weight or weight/volume basis.
5. 5 The herbicidal composition according to any one of the preceding claims wherein the salt forms of active ingredient (A) include as counterions alkali metal ions, alkaline earth metal ions, ammonium ions, quaternary ammonium ions, organic amines, or the conjugate bases of organic and inorganic acids.
6. 6 The herbicidal composition according to any one of the preceding claims wherein active ingredient (B) is microencapsulated.
7. 7 The herbicidal composition according to any one of the preceding claims wherein the composition is formulated as a granule, a powder, a paste, a concentrate, a gel, a solution, an emulsion, a dispersion, a suspension, or a controlled release form including a microcapsule. RECEIVED at IPONZ on 29 July 2011 8 The herbicidal composition according to any one of the preceding claims further comprising 1% to 99% customary formulation additives. 9 A formulation comprising a solid or liquid carrier and a herbicidal composition according to any one of the preceding claims. 10 A method of non-selectively controlling weeds which comprises applying to plants, parts of plants, plant seeds or to soil, a herbicidally effective amount of the synergistic herbicidal composition according to any one of the preceding claims characterised in that active ingredients (A) and (B) are present in synergistically effective ratios ranging from about 20:1 to about 1:20 and whereby, the composition is applied at a rate ranging from about 200 gai/ha to about 2,500 gai/ha, based on the combined rate of active ingredients (A) and (B). 11 The method according to claim 10 wherein the ratio of (A):(B) is 10:1 to 1:10. 12 The method according to claim 10 wherein the herbicidal composition is applied at a rate ranging from about 400 gai/ha to about about 2,000 gai/ha. 13 The method according any one of claims 10 to 12 wherein the herbicidal composition is applied at any stage of the crop cycle. 14 The method according to any one of claims 10 to 13 wherein the herbicidal composition is diluted with water before being applied to soil, plants and parts thereof by conventional means including spraying, sprinkling and wicking. 15 The method according to any one of claims 10 to 14 wherein active ingredients (A) and (B) of the herbicidal composition may be applied simultaneously or sequentially. RECEIVED at IPONZ on 29 July 2011 16 The method according to any one of claims 10 to 15 wherein active ingredients (A) and (B) of the herbicidal composition may be tank mixed prior to application. 17 The method according to any one of claims 10 to 16 wherein the synergistic herbicidal composition is used to non-selectively control monocotyledonous and dicotyledonous plants including annual and perennial grasses, broadleaf weeds, clovers, brush weeds and sedge. 18 A non-selective, synergistic herbicidal composition according to any one of claims 1 to 9 substantially as hereinbefore described with reference to any one of the accompanying Examples. 19 A method of non-selectively controlling weeds according to any one of claims 10 to 17 substantially as hereinbefore described with reference to any one of the accompanying Examples. END OF CLAIMS