AU2014203831B2 - Herbicidal compositions - Google Patents

Abstract

The invention relates to a selective, synergistic herbicidal composition comprising as active ingredients: (A) bentazone and/or one or more bentazone salts (B) flumetsulam, characterised in that (A) and (B) are present in synergistically effective ratios from about 10:1 to about 200:1 by weight. The synergistic interaction between bentazone and flumetsulam at the above ratios provides a surprisingly effective way to broaden weed control and control bigger weeds in the common forage species that in addition to various types of grasses, ryegrasses, legumes like clovers and lucerne, now include herbs like plantain and chicory etc, and mixtures of the above, all of which have differing herbicide tolerances. Page 23

Description

2014203831 14 Jul2014

NEW ZEALAND

Patents Act 1953

COMPLETE SPECIFICATION

HERBICIDAL COMPOSITIONS

We, ZELAM LTD, Hudson Road, New Plymouth 4341, New Zealand, do hereby declare this invention to be described in the following statement:-

Page 1

BACKGROUND 2014203831 14 Μ 2014

This invention relates to a herbicidal composition and more particularly to a synergistic herbicidal composition, to its method of preparation, and to its method of use.

Herbicides are used in different ways in agriculture and horticulture ranging from use of non-selective herbicides for total knockdown of existing herbage prior to cultivation and/or resowing, and control of unwanted vegetable around fruit trees etc, to the application of selective herbicides to established or recently planted crops to kill established weeds. Weed control is beneficial in mature pastures and essential in the early stages of pasture renewal and the establishment of seed crops.

In the early growth stages the crop may be more herbicide-sensitive. Broadleaf weed control, for example, can be very demanding and highly selective herbicidal active ingredients must be used. Bentazone is one such ingredient, a post-emergence contact herbicide originally developed for broadleaf and sedge weed control in broad acre crops such as rice, soya, cereals, rice, corn, and peanuts, which has found use in pastoral farming. As a selective herbicide bentazone is highly effective on only a few broadleaf weeds (chamomiles, cleavers, stinking mayweed, storksbill and Onehunga weed) with a lesser degree of control on black nightshade, chickweed, oxeye daisy, redroot, shepherd's purse, spurrey, thorn apple and wild turnip.

Mixing herbicidal active ingredients can be a good way to broaden weed control. However, choosing appropriate mixing partner for pastoral use is complicated by differing herbicide tolerances of the common forage species that now include various types of grasses, ryegrasses, legumes like clovers and lucerne, and herbs like plantain and chicory, and mixtures of the above.

Bentazone has been mixed with MCPA and/or MCPB for use on pasture. MCPB is used primarily for thistle control, and clover is more tolerant of MCPB than MCPA. However MCPB is less effective on other weeds and phenoxy-resistant thistles are emerging. Certain horticultural species such as wine grapes are so sensitive to phenoxy herbicides

Page 2 that products containing them cannot be safely used within 10 kilometres of a vineyard. Bentazone can be mixed with 2,4-DB for use on lucerne but this mixture is not completely safe on clover, and suffers the further disadvantage that 2,4DB is a phenoxy herbicide. 2014203831 14 M2014 A further problem with bentazone is finding a suitable mixing partner since there is a problem with antagonism between bentazone and some other herbicides such as certain sulfonyl ureas, 2,4-D amine, haloxyfop and sethoxydim. Herbicidal actives such as "fops” and “dims” for example would be ideal mixing partners for bentazone for use on crops like clovers, plantain and herb species owing to their grass selectivity.

Improved means of weed control in pasture are required to overcome shortcomings of existing mixtures and to cater for the growing use of new herbage species such lucerne, plantain and chicory.

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 the herbicidal active ingredients bentazone and flumetsulam interact synergistically when present in bentazone : flumetsulam ratios of from about 10:1 to about 200:1. This is surprising in view of the frequency of antagonistic interactions among herbicidal actives. The synergistic interaction between bentazone and

Page 3 flumetsulam at the above ratios provides a surprisingly effective way to broaden weed control and control bigger weeds in the common forage species that in addition to various types of grasses, ryegrasses, legumes like clovers and lucerne, now include herbs like plantain and chicory etc, and mixtures of the above, all of which have differing herbicide tolerances. 2014203831 14 Jul2014

Surprisingly, we have found that herbicidal compositions comprising synergistic ratios of bentazone and flumetsulam from about 10:1 to about 200:1 are particularly effective for weed control in a wide range of pasture types, fodder and seed crops, and turf.

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.

In one broad aspect this invention provides selective, synergistic herbicidal compositions comprising bentazone and flumetsulam as active ingredients.

In a further broad aspect this invention provides methods of formulating the selective, synergistic herbicidal compositions of the invention.

In a further broad aspect this invention provides a method of controlling weeds in agricultural crops, in particular pasture and fodder species, leguminous vegetable crops, seed crops and turf, using the selective, synergistic compositions of the invention.

DETAILED DESCRIPTION

This invention relates generally to combinations of herbicidal active ingredients and more particularly to synergistic combinations of the herbicidal active ingredients bentazone and flumetsulam formulated to provide more effective and broader control of weed species and/or increase crop safety and/or reduce herbicide residues.

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Preferably, the invention relates to combinations of herbicidal active ingredients and more particularly to synergistic combinations of the herbicidal active ingredients bentazone and flumetsulam formulated to provide more effective, broader and selective control of weed species and/or increase crop safety and/or reduce herbicide residues. 2014203831 14 Jul2014

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

The terms “herbicidal”, “herbicidal effectiveness”, etc, 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 that 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 “selective” herbicide is one which is sprayed over a crop to kill weeds without injury to the crop. A selective herbicide discriminates between target and non-target plants. A “non-selective herbicide” is used to kill all plants (crops plus weeds) in a desired target zone. In other words a non-selective herbicide doesn't discriminate between target and non-target plants.

Page 5 “Contact herbicides” destroy only the plant tissue in contact with the chemical. Generally, these are the fastest acting herbicides. They are less effective on perennial plants, which are able to regrow from rhizomes, roots or tubers. 2014203831 14 Jul2014 “Systemic herbicides” are translocated through the plant, either from foliar application down to the roots, or from soil application up to the leaves. They are capable of controlling perennial plants and may be slower acting but ultimately more effective than contact herbicides “Control” is the destruction of unwanted weeds, or the damage of them to the point where they are no longer competitive with the crop. “Suppression” is incomplete control still providing some economic benefit, such as reduced competition with the crop. “Crop Safety”, for selective herbicides, is the relative absence of damage or stress to the crop. Most selective herbicides cause some visible stress to crop plants, although this is usually transitory.

The term “synergistic” refers to a particular effect over and above an additive interaction. Generally a synergistic interaction is uncommon and restricted to particular conditions. Synergy is not displayed when individual components brought together are independently performing their routine function. Synergy may be calculated by various methods including those described by Y. Levy, M. Benderly, Y. Cohen, U. Gisi, and D. Bassand (“The Joint Action of Fungicides in Mixtures: Comparison of Two Methods for Synergy Calculation”, 1986, Bulletin OEPP, 16, 651-657), and by R. S. Colby (“Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, 1967, Weeds 15, 20-22).

Surprisingly, we have found that herbicidal compositions comprising ratios of bentazone and flumetsulam from about 10:1 to about 200:1 produce synergistic herbicidal effects, i.e., the herbicidal effectiveness as measured by inhibition of seed germination or weed

Page 6 growth by the combinations of active ingredients is unexpectedly greater than the expected effects calculated from the effects of individual active ingredients. The effective application rates required can be lowered as a result of this synergy making the resulting products and crop production systems more economical, and minimising or eliminating one or more of the previously mentioned problems. 2014203831 14 Jul2014

If the active compounds 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 compounds in the synergistic composition can be varied within a relatively wide range.

The ratios of bentazone to flumetsulam indicated in this disclosure do not in any way limit the scope of this invention, but are rather 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 ratios that produce a synergistic effect. The surprising aspect of the present invention is the unexpected synergy between bentazone and flumetsulam and their use in synergistic ratios as an effective herbicidal composition.

Bentazone (3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide) is a photosynthetic electron transport inhibitor at the photosystem II receptor site. It has the following physical properties (Pesticide Manual, 16th Ed.): Form Colorless crystals, M.p. 138°C, V.p. 5.4 x 103 mPa (20°C), Kow logP = 0.77 (pH 5), -0.46 (pH 7), -0.55 (pH 9), S.g. 1.41 (20°C), Solubility In water 570 mg/l (pH 7, 20°C). In acetone 1387 g/l, methanol 1061 g/l, ethyl acetate 582 g/l, dichloromethane 206 g/l, /i-heptane 0.5 mg/l. Stability Very resistant to hydrolysis in both acidic and alkaline media. Decomposed by sunlight. pKa 3.3 (24°C)

The invention includes all herbicidally active forms of bentazone including salts and partial salts prepared using 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. The most common commercial salt is

Page 7 bentazone sodium (sodium 3-isopropyl-3/-/-2,1,3-benzothiadiazin-4-olate 2,2-dioxide). The term “bentazone” refers to any one of these forms of bentazone. 2014203831 14 Μ 2014

Flumetsulam (2')6'-difluoro-5-methyl[1I2,4]triazolo[1,5-a]pyrimidine-2-sulfonanilide) has the following physical properties (Pesticide Manual, 16th Ed.): Form Off-white, odourless solid, M.p. 251-253°C, V.p. 3.7 x 10"7 mPa (25°C), Kow logP = -0.68 (25°C, unstated pH), S.g. 1.77 (21 °C), Solubility In water 47 mg/l (pH 2.5); solubility increases with pH. Very slightly soluble in acetone and methanol. Insoluble in hexane and xylene. Stability Aqueous photolysis DT50 6-12 mo. Soil photolysis DT50 3 mo. pKa4.6. F.p„ >93°C.

According to the invention, synergistic combinations of bentazone and flumetsulam may be found within the range of ratios from about 10:1 to about 200:1 by weight. More suitably Preferably, bentazone and flumetsulam are present in a ratio from about 15:1 to about 150:1 parts by weight. Still more suitably preferably, bentazone and flumetsulam are present in a ratio from about 20:1 to about 100:1 by weight.

The composition may comprise 0.1% to 80% bentazone and 0.1% to 8% flumetsulam 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.

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 a solution concentrate, an oil dispersion, a granule, a suspension, or a controlled release form including a microcapsule. More suitable formulation types are a soluble concentrate, an oil dispersible suspension, a water dispersible granule, and a suspension concentrate.

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In addition to bentazone and flumetsulam, 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 ingredients, 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. 2014203831 14 M2014 A preferred optional addition to the formulation is a surfactant thus removing the need for separate surfactant addition to the spray mixture. These may include non-ionic, amphoteric, anionic or cationic type surfactants such as, for example, alkyl polyglucosides, alkyl ethoxylates, alkyl sarcosinates, dioctyl sulfosuccinates, alkyl amine ethoxylates, organosilicones and a wide range of related surfactants, in mixture or alone. A further preferred optional addition to the formulation is an oil comprising a mineral oil, a vegetable oil, a vegetable oil ester or mixtures thereof. The optional oil component may be added to the diluted spray mixture in the form of a spraying oil, which commonly comprises about 95% oil, usually a mineral oil, and 5% emulsifier, or in the form of a crop oil concentrate, which commonly comprises about 80% oil and about 20% surfactant.

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

Page 9 herbicidal compositions. 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, or added to irrigation water. 2014203831 14 Jul2014

The composition may be applied at any stage of the crop cycle. Preferably the composition is used as a post-emergence herbicide for weed control during seed crop and pasture establishment, or is used on mature crops and pastures.

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”. In addition other additives such as plant growth regulators and fertilizers may be combined with the composition or dilutions thereof.

The active ingredients of the composition may be applied sequentially or, preferably, simultaneously. The active ingredients together with other additives are advantageously pre-formulated as a single mixture but 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 or oils during tank mixing. Bentazone and flumetsulam may be applied sequentially, in any order and in any timescale, suitably within a one week period, more suitably within a 24 hour period, and, preferably, within one hour.

The use rate for the herbicidal 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 50 gram active ingredient per hectare (gai/ha) to about 2,750 gai/ha, based on the combined rate of active ingredients. Suitable use rates for the bentazone component range from about 50 gai/ha to about 2,500 gai/ha. Suitable use rates for the flumetsulam component range from about 1 gai/ha to about 250 gai/ha.

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More suitably the herbicidal composition is applied at a rate ranging from about 100 gram active ingredient per hectare (gai/ha) to about 2,000 gai/ha, based on the combined rate of active ingredients. 2014203831 14 Jul2014

Still more suitably the herbicidal composition is applied at a rate ranging from about 100 gram active ingredient per hectare (gai/ha) to about 1,500 gai/ha, based on the combined rate of active ingredients.

Compositions containing flumetsulam may benefit from the addition of crop oil (spraying oil) applied at a rate of 500 ml - 2,000 ml/ha.

The invention may be used where the crop is one or more of any species of grass, legume or herb grown for forage, seed or vegetable production. This includes a wide variety of pasture types, turf, fodder or vegetable legumes, and seed crops thereof, including but not limited to grasses, ryegrasses, legumes and herb species. Preferred crops are grass and ryegrass based pastures, clovers, chicory, lucerne, plantain, peas, and seed crops thereof. Many of these are grown in mixture.

The invention may be used to control a broad range of agriculturally important weeds including monocotyledonous and dicotyledonous weeds. In some situations a plant species such as plantain may be considered a “weed” and in other situations it may be considered the crop or one of several crop species.

The composition may be used to control various weeds including but not limited to amaranthus (redroot, Amaranthus powellii), annual buttercup (Ranunculus parviflorus), black nightshade {Solarium nigrum), broad-leaved dock {Rumex obtusifolius), Californian thistle (Cirsium arvense), chamomiles (Anthemis spp and Matricaria spp.), chickweed {Stellaria media), cleavers (Galium aparine), common sorrel {Rumex acetosa), creeping yellow cress {Rorippa sylvestris), dandelion {Taraxacum officinale), dandelion {Taraxacum officinale), fathen {Chenopodium album), field madder {Sherardia arvensis), field pansy {Viola arvensis), giant buttercup {Ranunculus acris), hairy nightshade {Solanum

Page 11 physalifolium), hawkbit (Leontodon taraxacoides), hedge mustard (Sisymbrium officinale), henbit (Lamium amplexicaule), inkweed (Phytolacca octandra), mallow (Malva ssp.), nettle (Urtica urens), nodding thistle (Carduus nutans), Onehunga weed (prickleweed, Soliva sessilis), oxeye daisy (Chrysanthemum leucanthemum), plantain (Plantago ssp.), prickly sow thistle (Sonchus asper ssp. glaucescens), Scotch thistle (Cirsium vulgare), scrambling speedwell (Veronica persica), shepherd's purse (Capsella bursa-pastoris), spurrey (Spergula arvensis), stinking mayweed (Anthemis cotula), storksbill (Erodium cicutarium), thorn apple (Datura stramonium), twincress (Coronopus didymus), wild radish (Raphanus raphanistrum), wild turnip (Brassica rapa sssp. sylvestris), willow weed (Persicaria persicaria), wireweed (Polygonum aviculare), and yellow gromwell (Amsinckia calycina). 2014203831 14 Μ 2014

The following examples and the particular proportions set forth are intended to be illustrative only and are thus non-limiting. EXAMPLE 1. Bentazone flumetsulam soluble concentrate

Dissolve 495 g flumetsulam tech in 275 g pre-warmed N-methyl pyrrolidone. Add 140 g of water then, with vigorous stirring, add in parts 495 g bentazone tech followed by proportional amounts of isopropyl amine. Adjust the pH to 6.5-7.5 with the final portion of isopropyl amine (total weight 275 g), then make up to 1 L with water. The resulting SL comprises 480 g/L bentazone and 17 g/L flumetsulam, and can be diluted with water ready for use. EXAMPLE 2. Bentazone sodium - flumetsulam soluble concentrate

Dissolve 4.3 g flumetsulam tech in 100 g pre-warmed N-methyl pyrrolidone. In a separate vessel dissolve 542 g bentazone sodium tech in 600 g water with vigorous stirring. Add the flumetsulam solution to the bentazone once it has dissolved, then make up to 1 L with water. The resulting SL comprises 525 g/L bentazone sodium and 4.2 g/L flumetsulam, and can be diluted with water ready for use. EXAMPLE 3. Bentazone sodium - flumetsulam oil dispersion

To 100 g paraffinic oil and 400 g methyl oleate disperse with high shear mixing 35 g oil-swellable clay. Add 150 g non-ionic dispersant emulsifier then disperse 250 g bentazone

Page 12 sodium tech and 7.7 g flumetsulam tech. Finally mill the mixture until the average particle size lies within the range from about 2 pm to about 5 pm to produce an OD containing 240 g/L bentazone sodium and 7.5 g/L flumetsulam that can be diluted with water ready for use. 2014203831 14 Μ 2014 EXAMPLE 4. Bentazone sodium - flumetsulam water dispersible granule

Using a dough mixer thoroughly blend 500 g bentazone sodium tech and 15.3 g flumetsulam tech along with 80 g Morewet 425, 20 g Morewet EFW and 363 g of Kaolin. Blend with a controlled amount of water to form an extrudable dough, extrude through a basket extruder, dry gently and size to produce a WG containing 480 g/kg bentazone sodium and 15 g/kg flumetsulam that can be dispersed into water ready for use. EXAMPLE 5. Bentazone acid flumetsulam suspension concentrate

Combine 25 g sodium polynaphthalene sulfonate and 5 g non-ionic wetting agent in 386 g water and 30 g propylene glycol. Mix in 75 g of an aqueous slurry comprising 8% VEEGUM (magnesium aluminium silicate) then add 0.4 Gensil 2000 and 0.2 g 14% methylchloroisothiazolinone. Slowly add 495 g bentazone tech and 17.4 g flumetsulam tech then add 2 g citric acid to adjust the pH to 6 - 7. Pump the resulting mill concentrate through a Dyno mill continuous ball mill to reduce the particle size below 5 pm. Finally add 100 g of 1.5% pre-gelled xanthan gum, and make up to 1 L. The resulting suspension concentrate containing 480 g/L bentazone and 17 g/L flumetsulam can be diluted with water ready for use. EXAMPLE 6. Bentazone : flumetsulam synergy

Synergistic interactions between bentazone and flumetsulam were demonstrated by the herbicidal effects on root growth in germinated seeds. Five-fold dilutions of bentazone, flumetsulam or mixtures of the two herbicides were pipetted onto 90 mm diameter Whatman # 1 filter papers placed in Petrie dishes (5 ml per dish). Water was used in untreated controls. Twelve seeds were distributed evenly on each filter paper and dishes incubated at 21 °C. Root lengths were measured after 3-7 days depending on the seed type. Data from the two shortest or from ungerminated seedlings were discarded. Percent inhibition (herbicide-treated root length/untreated root length) was measured for at least

Page 13 five herbicide dilutions. End point values (EC50, the herbicide concentration producing 50% inhibition of seedling growth) were calculated by regression analysis of dose response data using the GraphPad Prism software package (GraphPad Software, Inc., 5755 Oberlin Drive #110, San Diego, CA 92121, USA), and are expressed in ppm. Synergy was determined by the “Wadley method” for similar joint action as published by Y. Levy, M. Benderly, Y. Cohen, U. Gisi, and D. Bassand (“The joint action of fungicides in mixtures: comparison of two methods for synergy calculation”, 1986, Bulletin OEPP 16, 651-657), according to the formulae: 2014203831 14 Jul2014 1. ED(exp) = (a + jb)/(a/EDA + blEDB), in which, EDa is the concentration in ppm of (A), acting alone, which produced an end point, EDb is the concentration in ppm of (B), acting alone, which produced an end point, a and b are the proportions of (A) and (B) in the mixture, and ED(exp) is the expected equally effective concentration in ppm of (A) and (B), acting together, in the proportions a and b, and 2. SF = ED(exp)/ED(obs), in which, SF is the synergy factor, and ED(obs) is the observed equally effective concentration in ppm of (A) and (B), acting together, in the proportions a and b.

If SF > 1, there is synergistic interaction between the herbicides, if SF < 1, there is antagonistic interaction, and if SF = 1, there is additive action (i.e. similar joint action).

Combined action of bentazone (as sodium salt) and flumetsulam on seed germination.

Herbicide EC50 (obs) EC50 (exp) SF Tomato (7 days) Bentazone 85.8 200 : 1 51.7 85.0 1.65 100 : 1 69.9 84.3 1.21 50 : 1 37.2 82.8 2.23 20 : 1 21.0 78.8 3.75 Flumetsulam 29.8

Page 14 2014203831 14 Jul2014

Herbicide EC5o(obs) EC50(exp) SF Herbicide EC5o(obs) EC5o(exp) SF Cucumber (Expt 1, 3 days) Radish (3 days) Bentazone 467 Bentazone 303 28 : 1 55.8 98.9 1.77 28 : 1 13.3 25.6 1.93 10 : 1 90.2 43.2 0.48 10 : 1 12.4 10.3 0.83 1 : 1 28.9 8.5 0.29 1 : 1 1.9 1.9 1.00 Flumetsulam 4.3 Flumetsulam 1.0 Cucumber (Expt 2, 3 days) Stachys (5 days) Bentazone 679 Bentazone 275 200 : 1 244 520 2.13 100 : 1 52.9 202.4 3.83 100 : 1 192 423 2.20 50 : 1 79.5 161.0 2.02 50 : 1 234 308 1.32 28 : 1 18.9 122.5 6.47 20 : 1 143 173 1.22 20 : 1 17.9 101.2 5.64 Flumetsulam 10.9 Flumetsulam 7.4 Mustard (3 days) Turnip (5 days) Bentazone 82 Bentazone 820 200 : 1 7.9 21.6 2.73 200 : 1 273 795 2.91 100 : 1 0.9 12.5 13.66 100 : 1 177 772 4.36 50 : 1 2.6 6.8 2.66 50 : 1 278 729 2.62 20 : 1 1.0 2.9 2.85 20 : 1 248 629 2.54 Flumetsulam 0.15 Flumetsulam 111

Weed species represented in these tests include those belonging to the Cucurbitaceae (cucumber), Brassicaceae such as hedge mustard, shepherd’s purse, wild radish and wild turnip (radish, mustard, turnip), Lamiaceae such as henbit (Stachys), and Solanaceae such as the nightshade family (tomato).

The following field trials were performed with a randomized block design with four replicates. Analysis of variance was performed using the Agricultural Research Manager software package (Gylling Data Management, Inc.). Means followed by the same letter do not significantly differ (P = 0.05, Duncan’s New MRT, unrelated treatments omitted for clarity). Flumetsulam treatments contained approx. 500 ml/100 L spraying oil. Water rates 250-300 L/Ha.

Page 15 EXAMPLE 7. Weed control in young pasture 2014203831 14 Μ 2014 A young pasture in Hawkes Bay sown on 5 April 2011 was sprayed 20 days post emergence (perennial ryegrass, Lolium perenne, 7 leaf stage, and white clover, Trifolium repens, 2 trifoliate stage) then assessed at 29 and 43 days after application (DAA). A 28:1 bentazone flumetsulam mixture provided excellent control of weeds with acceptable crop damage given the early stage of crop development. Dandelion is not controlled by bentazone or flumetsulam alone.

Treatment Ryegrass (g/m2) 29 DAA Clover {% suppression' 43 DAA Dandelion (% control) 19 DAA Black night shade (count) 43 DAA Flumetsulam 50 g/Ha 99.6 abc 30.0 a 63.8 be 0.0 b Bentazone 720 g/Ha + Flumetsulam 25 g/Ha 77.8 b-e 15.0 be 90.0 a 0.5 b Bentazone 1440 g/Ha + Flumetsulam 50 g/Ha 51.7 e 31.3 a 100.0 a 1.0 b Bentazone 1440 g/Ha 75.6 b-e 6.3 de 90.0 a 0.8 b Untreated control 123.7 a 0.0 e 0.0 f 40.8 a EXAMPLE 7. Weed control in young pasture A young pasture in Canterbury was sprayed 30 April 2011 (perennial ryegrass, 4 leaf, and white clover, 2 trifoliate) then assessed 17 DAA. A 28:1 bentazone : flumetsulam mixture gave minimal crop damage, good suppression of plantain, and controlled Nodding thistle as well as a standard bentazone MCPB thistle control mixture, but at a much lower total rate of herbicidal active ingredients.

Treatment Ryegrass (g/m2) Clover (g/m2) Plantain (% stunting) Nodding thistle (g/m2) Flumetsulam 50 g/Ha 181 a 4.91 a 28.8 ab 1.17 a Bentazone 1440 g/Ha + Flumetsulam 50 g/Ha 206 a 5.74 a 23.8 be 0.00 a Bentazone 1400 g/Ha + MCPB 1400 g/Ha 222 a 3.91 a 33.8 a 0.00 a Bentazone 1440 g/Ha 219 a 6.08 a 0.0 d 0.08 a Untreated control 240 a 4.58 a 0.0 d 4.58 a

Page 16 EXAMPLE 8. Weed control in young pasture 2014203831 14 Μ 2014 A young pasture in Hawkes Bay was sprayed 1 May 2011 (perennial ryegrass, 3 tillers, and white clover, 1st side shoot). A 28:1 bentazone : flumetsulam mixture gave minimal ryegrass damage, good control and field madder and hawkbit, and controlled Nodding thistle as well as a standard bentazone MCPB thistle control mixture, but at a much lower total rate of herbicidal active ingredients. T reatment Ryegrass (g/m2) 48 DAA Field Madder ;% chem. effect 48 DAA Hawkbit (g/m2) 48 DAA Nodding thistle (count) 78 DAA Flumetsulam 50 g/Ha 83.0 ab 55.0 be 1.31 b 20.5 ede Bentazone 1440 g/Ha + Flumetsulam 50 g/Ha 65.8 bed 70.0 ab 0.17 b 1.3 e Bentazone 1400 g/Ha + MCPB 1400 g/Ha 58.0 cd 90.0 a 0.11 b 1.5 e Bentazone 1440 g/Ha 50.3 d 32.5 c 0.19 b 8.0 de Untreated control 90.3 a 0.0 d 3.91 a 315 a EXAMPLE 9. Control of phenoxy-resistant thistles A 5 week old pasture in Hawkes Bay was sprayed 7 May 2011 (perennial ryegrass, 3 tillers, and white clover, 5 leaf) and assessed 39 DAA. An MCPB MCPA mixture did not control nodding thistles alone or in combination with flumetsulam indicating phenoxy-resistance, which is common in Hawkes Bay. A 28:1 bentazone : flumetsulam mixture gave full control of these thistles, along with Scotch thistles when applied at a relatively low rate.

Treatment Nodding thistles 2-6 leaf (count per 24 m2 plot) Scotch thistles 2-4 leaf (count per 24 m2 plot) Flumetsulam 50 g/Ha 4.8 b 1.0 b MCPB 1125 g/Ha + MCPA 75 g/Ha 12.3 ab 0.3 b Flumetsulam 65 g/Ha + MCPB 1125 g/Ha + MCPA 75 g/Ha 2.0 b 0.0 b Bentazone 720 g/Ha + Flumetsulam 25 g/Ha 0.0 b 0.0 b Untreated control 25.8 a 4.3 a

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Example 10. Weed control in a plantain crop 2014203831 14 Μ 2014

Narrow leaf plantain (Plantago lanceolata) planted in Taranaki in early May 2013 was sprayed June 14 2013 when the crop was at 50% two leaf, 50% four leaf. Quadrat weighings 49 DAA showed a severe reduction in plantain growth with bentazone and flumetsulam present in a 28:1 ratio but less severe reductions at higher ratios. By mid September the crop was recovering well, particularly at the higher bentazone flumetsulam ratios. Excellent weed control was exhibited at all ratios.

Treatment Herbicide g/Ha Ratio Plantain g/m2 49 DAA Willow weed g/m2 49 DAA Chick weed g/m2 49 DAA Fathen count 60 DAA Plantain g/m2 96 DAA Spurrey g/m2 96 DAA Bentazone 1,000 + Flumetsulam 15 66.7 164 b 0.00 a 0.00 a 0.0 b 854 ab 1 b Bentazone 1,000 + Flumetsulam 20 50.0 204 b 0.00 a 0.00 a 0.1 b 931 ab 12 b Bentazone 1,000 + Flumetsulam 25 40.0 105 be 0.00 a 0.00 a 0.1 b 836 ab 1 b Bentazone 960 + Flumetsulam 34 28.2 49 c 0.00 a 0.00 a 0.3 b 715 b 2 b Untreated 600 a 0.65 a 7.10 a 10.8 a 1334 a 717 a

It will be appreciated that the compositions and uses provided are examples only and that other selective, synergistic herbicidal compositions comprising bentazone and flumetsulam, and uses thereof, may be contemplated.

MODIFICATIONS AND VARIATIONS

Having generally described this invention, including the best mode thereof, those skilled in the art will appreciate that the present invention contemplates the embodiments of this invention as defined in the following claims, and equivalents thereof. However, those skilled in the art will appreciate that the scope of this invention should not be measured merely by the specific embodiments exemplified herein.

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Those skilled in the art will also appreciate that more sophisticated technological advances will likely appear subsequent to the filing of this document with the Patent Office. To the extent that these later developed improvements embody the operative principles at the heart of the present disclosure, those improvements are likewise considered to come within the ambit of the following claims. 2014203831 14 Jul2014

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.

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 also fall within the ambit of the invention.

In a preferred embodiment the invention includes within its scope a kit of parts, the kit of parts providing for a selective herbicidal composition comprising in synergistic proportions in separate containers or as separate compartments within the same container a combination of: (A) bentazone and/or one or more bentazone salts, and (B) flumetsulam.

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Claims (22)

1. WHAT I/WE CLAIM IS:

   1. A selective, synergistic herbicidal composition comprising as active ingredients: (A) bentazone and/or one or more bentazone salts (B) flumetsulam, characterised in that (A) and (B) are present in synergistically effective ratios from about 20:1 to about 200:1 by weight.
2. 2. The selective synergistic herbicidal composition according to claim 1 further characterised in that the composition is formulated as a concentrate to be applied, on dilution, at an application rate ranging from about 50 gai/Ha to about 2,750 gai/Ha based on the combined weights of (A) and (B).
3. 3. The selective synergistic herbicidal composition according to claim 1 or claim 2 whereby the composition is applied at a rate ranging from about 100 gai/ha to about 2,000 gai/ha based on the combined weights of (A) and (B).
4. 4. The selective synergistic herbicidal composition according to any one of claims 1 to 3 wherein the weight ratio of (A) to (B) is from about 20:1 to about 150:1.
5. 5. The selective synergistic herbicidal herbicidal composition according to any one of the preceding claims wherein the weight ratio of (A) to (B) is from about 20:1 to about 100:1.
6. 6. The selective synergistic herbicidal composition according to any one of the preceding claims comprising 0.1% to 80% (A) and 0.1% to 10% (B) on a weight/weight basis or a weight/volume basis.
7. 7. The selective synergistic herbicidal composition according to any one of the preceding claims wherein the composition is formulated as a solution concentrate, an oil dispersion, a granule, a suspension concentrate, or a microcapsule.
8. 8. The selective synergistic herbicidal composition according to any one of the preceding claims further comprising 1 to 99% on a weight/weight basis or a weight/volume basis of customary formulation additives.
9. 9. The selective synergistic herbicidal composition according to claim 8 wherein the customary formulation additive is an oil selected from a mineral oil, a vegetable oil, a vegetable oil ester and mixtures thereof.
10. 10. The selective synergistic herbicidal composition according to claim 8 or claim 9 wherein the customary formulation additive is a non-ionic, amphoteric, anionic or cationic type surfactant.
11. 11. The selective synergistic herbicidal composition according to claim 10 wherein the surfactant is an alkyl polyglucoside, alkyl ethoxylate, alkyl sarcosinate, dioctyl sulfosuccinate, alkyl amine ethoxylate or organosilicone and mixtures thereof.
12. 12. The selective synergistic herbicidal composition according to any one of the preceding claims further comprising a solid or liquid carrier.
13. 13. A method for the selective control or suppression of weeds which comprises applying to plants, parts of plants, plant seeds or to soil a herbicidally effective amount of the synergistic composition accordingly to any of the preceding claims characterised in that active ingredients (A) bentazone and/or one or more bentazone salts and (B) flumetsulam are present in synergistically effective ratios from about 20:1 to about 200:1 by weight and whereby the composition is applied at a rate ranging from about 50 gai/ha to about 2,750 gai/ha based on the combined weights of (A) and (B).
14. 14. The method according to claim 13 wherein the weight ratio of (A) to (B) is from about 20:1 to about 150:1.
15. 15. The method according to claim 13 or claim 14 wherein the weight ratio of (A) to (B) is from about 20:1 to about 100:1.
16. 16. The method according to any one of claims 13 to 15 wherein the herbicidal composition is applied at any stage of the crop cycle.
17. 17. The method according to any one of claims 13 to 16 wherein the crop is one or more of any species of grass, legume or herb grown for forage, seed or vegetable production.
18. 18. The method according to any one of claims 13 to 17 wherein the herbicidal composition is diluted with water before being applied to plants, parts of plants, plant seeds or to soil by conventional means including spraying, sprinkling and wicking.
19. 19. The method according to any one of claims 13 to 18 wherein (A) and (B) may be applied simultaneously or sequentially.
20. 20. The method according to any one of claims 13 to 19 wherein (A) and (B) may be tank mixed prior to application. 21 The method according to any one of claims 13 to 20 wherein the selective, synergistic herbicidal composition is used to selectively control monocotyledonous and dicotyledonous weeds.
21. 22. A selective, synergistic herbicidal composition according to any one of claims 1 to 12 substantially as hereinbefore described with reference to any one of the accompanying examples.
22. 23. A method of selectively controlling weeds according to any one of claims 13 to 21 substantially as hereinbefore described with reference to any one of the accompanying examples. END OF CLAIMS