NZ594861A - Synergistic Fungicidal Compositions - Google Patents

Abstract

Disclosed is a synergistic fungicidal composition comprising as active ingredients fludioxonil and fluazinam, characterised in that fludioxonil and fluazinam are present in synergistically effective ratios from about 5:1 to about 1:5 by weight.

Description

Patents Form # 5 NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION AFTER PROVISIONAL NO.: 594861 PRIORITY DATE : 29 August 2011 TITLE : Synergistic Fungicidal Composition We, ZELAM LIMITED Address: 15 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: 402060NZ_Cap_20120117_940_EMM.doc FEE CODE 1050 FIELD OF THE INVENTION This invention relates to a synergistic fungicidal composition for the control of fungal diseases on horticultural crops and vegetables, to its method of preparation, and its method of use.

BACKGROUND OF THE INVENTION Fungal diseases are the major cause of crop losses in modern agriculture. Modern synthetic fungicides are the most effective means of combating fungal phytopathogens and boosting productivity. A particular challenge for producers is minimising residues of pesticidal active ingredients in fresh produce and manufactured products such as beverages, jams, frozen vegetables, canned fruit, etc.

Maximum residue limits (MRLs) for pesticides are set by countries and states for individual crops. The MRL determines the timing (and amount) of the last application of pesticide to a crop. This is managed practically by imposing a "withholding period", i.e. the minimum interval between the last pesticide application and the time of harvest. A suitable withholding period is determined empirically for each crop and is based on the half life of the pesticidal active ingredient (or metabolites thereof) on the crop in question. In the case of fungal diseases the grower will spray the last fungicide in the hope that the fungal inoculum is reduced enough to carry the crop through to harvest without unacceptable levels of disease. For control of some diseases other fungicide timings are also important, e.g. control of botrytis spores in grapes at flowering.

Advancing technology is enabling analytical laboratories to detect residues in produce at ever decreasing concentrations. This is having the effect of driving down MRLs, which in turn is increasing product withholding periods. Therefore there is a need for increasingly effective fungicidal compositions that will achieve effective disease control throughout the growing period, and especially during the withholding period.

Management of fungicide resistance is another ongoing challenge. Fungicides with a site-specific mode of action are more likely to develop resistance, or develop resistance more quickly than those with multi-site modes of action. Resistance also varies based on pathogen, life cycle stages and rates of reproduction. Fungicide resistance in the field is caused or enhanced by a number of factors including overuse of a single fungicide or of fungicides with the same mode of action, fungicide use at times (e.g. post infection rather than pre infection) or under production conditions (e.g. susceptible crop varieties, crop stress) when the number of individuals exposed to selection pressure is high, absence of crop rotation, inadequate spray coverage, suboptimal application rates, etc. 2 Use of a fungicide combining two (or more) active ingredients has the joint effects of better resistance management, broader spectrum of activity, lowering of rates (without increasing risk of resistance) and thereby reducing individual component residues in crops at harvest.

Fludioxonil is a phenylpyrrole fungicide targeting signal transduction, specifically MAP/Histidine-kinase in osmotic signal transduction (FRAC Code 12, Mode of Action Code E2). Fludioxonil is considered to have a low to medium risk of developing resistance. Fludioxonil is relatively residual. For example in New Zealand fludioxonil has a MRL of 1 mg/kg on grapes that is achieved with 56 day withholding period.

Fluazinam is a pyridine fungicide (in particular a 2,6-dinitrophenyl crotonate) targeting respiration, specifically an uncoupler of oxidative phosphorylation (FRAC code 29, Mode of Action Code C5). Fluazinam is considered to have a low risk of developing resistance. Fluazinam is relatively short acting. In New Zealand fluazinam has a MRL of 1 mg/kg on grapes that is achieved with a 28 day withholding period.

The applicants have discovered that fludioxonil and fluazinam interact in a synergistic manner with respect to fungicidal activity. This is entirely unexpected and surprising when it is considered that the active ingredients have a different biochemical mode of action and fludioxonil is a long acting residual fungicide and fluazinam is a relatively short acting fungicide. As a result of the unexpected synergy application rates can be lowered beyond what is possible with an additive interaction between the actives. This enables application of the composition later in the crop production cycle without risk of exceeding MRLs at harvest. This in turn gives the grower greater certainty that the crop will reach maturity beyond the last application with a low risk of infection. The net effect is more effective disease control at reduced cost.

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. 3 OBJECT OF THE INVENTION It is an object of the invention to provide an improved fungicidal composition and/or preparative method thereof and/or use thereof, and at least to provide the public with a useful choice.

SUMMARY OF THE INVENTION In one broad aspect this invention provides a synergistic fungicidal composition suitable for use as an agricultural fungicide comprising fludioxonil and fluazinam as active ingredients.

In a first surprising aspect we have found synergistic, fungicidal compositions comprising as active ingredients: (A) at least one phenylpyrrole fungicide, and (B) at least one pyrine fungicide and/or salts thereof, And wherein components (A) and (B) are in synergistic ratios.

In a second surprising aspect the invention provides for a synergistic fungicidal composition comprising as active ingredients: (A) fludioxonil and (B) fluazinam, characterised in that active ingredients (A) and (B) are present in synergisticaliy effective ratios from about 20:1 to about 1:20 by weight.

Preferably, the composition is applied at a rate ranging from about 5 gai/ha to about 2,500 gai/ha based on the combined weights of fludioxonil and fluazinam.

In a third aspect the invention provides for a synergistic fungicidal composition comprising as active ingredients: (A) fludioxonil and (B) fluazinam, 4 when used to selectively control or suppress fungal growth, the composition being characterised in that active ingredients (A) and (B) are present in synergisticaliy effective ratios from about 20:1 to about 1:20 by weight and whereby the composition is applied at a rate ranging from about 5 gai/ha to about 2,500 gai/ha based on the combined weights of fludioxonil and fluazinam.

Accordingly, in a still further broad aspect this invention provides compositions comprising synergistic, selective fungicidal compositions comprising active ingredients (A) and (B) and, optionally, further comprising a third active ingredient being (C) a biocide selected from one or more of the group comprising: fungicides, insecticides, and bactericides. Preferably ingredient (C) is one or more insecticides In a further aspect the fungicidal composition comprises fludioxonil and fluazinam as active ingredients in fludioxonil: fluazinam weight ratios from about 20 :1 to about 1 : 20, sufficient to provide a synergistic fungicidal activity when used against fungal pathogens of plants.

In a further broad aspect this invention provides methods of formulating the synergistic fungicidal compositions comprising fludioxonil and fluazinam.

In a further broad aspect this invention provides a method of controlling fungal diseases, which comprises applying to plants, parts of plants, plant seeds, seedlings, or to soil, fungicidally effective amounts of the fungicidal composition of the invention.

DETAILED DESCRIPTION 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 term "fungicidal" encompasses all effects on fungi including but not limited to the destruction or killing of fungi, a defined logarithmic reduction, a partial or complete suppression or inhibition of growth, inhibition of germination, and the like. The term "fungicidally effective amount" indicates the quantity or application rate of a fungicidal composition or of a fungicidal active ingredient which is capable of producing any one or more such effects.

The term "synergistic" refers to a particular phenomenon that occurs when the observed fungicidal effect of a mixture of active ingredients is unexpectedly greater than might be expected from the sum of the observed fungicidal effects of the active ingredients administered separately. In contrast an antagonistic effect refers to the situation whereby two or more components produce a combined effect which is less than the sum of their individual parts, and an additive effect refers to the situation where a combined effects is equal to the sum of their individual parts.

Synergy may be measured in various ways, generally based on fungicide concentrations that produce a defined end point in measured fungal growth, or in measured or otherwise evaluated effects resulting from the fungal growth including the effects of fungal growth on plants. Examples of such measurements or evaluated effects include colony diameter, percentage germination, growth rate, percentage plant part affected, incidence of effects of plant parts, etc. Any of these and other parameters can be enumerated using an instrument and/or evaluated manually or visually and assigned to linear or non-linear rating scales.

Methods that may be used to calculate synergy include 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), by F. C. Kull, P. C. Eisman, H. D. Sylwestrowicz, and R. L. Mayer ("Mixtures of Quaternary Ammonium Compounds and Long-chain Fatty Acids as Antifungal Agents", 1961, Applied Microbiology, 9, 538-541), and 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, X represents the percent inhibition of growth by fungicide A at x grams of active ingredient per hectare (gai/ha), Y represents the percent inhibition of growth by fungicide B at y gai/ha, and E represents the expected percent inhibition of growth by fungicides A + B in combination at x + y gai/ha, respectively.

When the observed percent inhibition of growth by fungicides A + B is greater than E (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. 6 Fludioxonil (4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1/-/-pyrrole-3-carbonitrile) has the following properties: solubility at 25°C in grams/litre: water 1.8 x 10"3, acetone 190, dichloromethane 7.3, ethanol 44, ethyl acetate 86, n-hexane 1 x 10"3, methanol 42, n-octanol 20, toluene 2.7; stable to acid, alkali and heat; vapour pressure 3.9 x 10"7 Pa at 25°C; Kow (log P) 4.12; Henry's law constant 5.4 x 10"5 Pa.m3.mol"1. There is no dissociation in water at environmentally relevant pH values. Formulation types for fludioxonil as a single active ingredient include DS, FS, SC. WG and WP.

Fluazinam (3-chloro-A/-(3-chloro-5-trifluoromethyl-2-pyridyl)-a,a,a~trifluoro-2,6-dinitro-p-toluidine) has the following properties: solubility at 25°C in grams/litre: water 1.35 x 10"4 (pH 7), acetone 853, dichloromethane 675, ethyl acetate 722, ethyl ether 231, n-hexane 8, methanol 192, n-octanol 41, toluene 451; stable to acid, alkali and heat; vapour pressure 7.5 x 10"3 at 25°C; Kow (log P) 4.03; Henry's law constant 25.9 Pa m3.mol"1. The dissociation constant (pKa) for fluazinam is 7.34. Formulation types for fluazinam as a single active ingredient include DP, SC and WP.

According to the invention, synergistic combinations of fludioxonil and fluazinam may be found when the relative amounts of fludioxonil and fluazinam expressed as a ratio fludioxonil: fluazinam are present within the range from about 20 :1 to about 1 : 20 parts by weight.

Preferably fludioxonil and fluazinam are present in a ratio from about 10 :1 to about 1:10 parts by weight. More preferably fludioxonil and fluazinam are present in a ratio from about 5 :1 to about 1 : 5 parts by weight. Still more suitably fludioxonil and fluazinam are present in a ratio from about 3 :1 to about 1 : 3 parts by weight.

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 fludioxonil to fluazinam indicated in this disclosure do not in anyway limit the scope of this invention, but rather are mentioned as a guide, a person of ordinary skill in the art being capable of carrying out complementary experiments in order to find other values of the ratios of active ingredients which produce a synergistic effect. 7 The synergistic fungicidal composition comprising fludioxonil and fluazinam may be used to control a broad range of fungal pathogens including but not limited to Alternaria solani (early blight), Aspergillus carbonarius, Botrytis cinerea (grey mould), Colletotrichum acutatum (anthracnose), Fusarium sp. (root rot), Helminthosporium sp. (eyespot), Microdochium nivale (pink snow mold), Peronospora farinose (downy mildew), Phomopsis viticola (dead arm), Phytophthora infestans (late blight), Plasmodiophora brassicae (clubroot), Rhizoctonia solani (damping off), Rhizopus stolonifer(leak), Sclerotinia sclerotiorum (white mould), Septoria sp. (leaf spot), Spongospora subterranea (powdery scab), and Tilletia caries (bunt).

The composition may comprise 0.1% to 60% fludioxonil and 0.1% to 60% fluazinam 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.

Formulation types and methods of manufacture developed for crop protection purposes are generally used for preservatives for timber, wood and other biodegradable products. These 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 fungicidal composition include, but are not limited to, a powder, a granule, a concentrate, a gel, a solution, an emulsion, a dispersion, a suspension, or a controlled release form including a microcapsule. Preferred formulation types are a suspension concentrate, an emulsion, a granule, a powder and a capsule suspension. Advantageously, the formulation is a liquid thus minimising exposure of users to the hazards of powders and dusts.

In addition to fludioxonil and fluazinam, the fungicidal 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, antifreeze agents, anti-caking agents, lubricants, stickers, binders, glues, resins, complexing agents, chelating agents, crystallization inhibitors, dyes, activators, synergists, safeners, rain proofers, UV protectants, fertilizers, micronutrients, and the like. 8 Further biocidal active ingredients may be combined with the fungicidal active ingredients of the composition including other fungicides, insecticides, bactericides, and the like. Preferably the additional biocidal ingredient is one or more insecticides.

Compositions are formulated using known methods by dissolving, dispersing, finely dividing, slurrying, blending, 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. In addition fludioxonil and/or fluazinam may be microencapsulated, separately or together, prior to mixing with other formulation additives. Further details of suitable methods of manufacture of the composition are provided in the examples.

Where applicable to the compositions formulated using the known methods referred to above and as provided in methods of the examples, the mean particle size as determined for example using a laser diffraction particle size analyser after dilution into water, is from about 0.1 microns to about 50 microns.

Preferably the mean particle size is from about 0.1 microns to about 20 microns. Still more preferably the mean particle size is from about 0.2 microns to about 5 microns.

The invention provides a method of fungal diseases, which comprises applying to plants, parts of plants, plant seeds or to soil, fungicidally effective amounts of the synergistic fungicidal compositions comprising fludioxonil and fluazinam.

The composition may be applied at any stage of the crop cycle excluding the withholding period.

In general the composition may be diluted into a carrier and applied by conventional means to plants, parts of plants, plant seeds, seedlings, or to soil. Water is the carrier of choice and the composition may be mixed into water and applied by spraying, sprinkling, irrigating, coating, wicking, etc. In the case of seeds known seed treatment methods are to be used.

Other biocidal active ingredients may be combined with the fungicidal composition, and may include other fungicides, bactericides, insecticides, nematicides, and the like. These active ingredients may be added as a "tank mixture". 9 Fludioxonil and fluazinam may be applied sequentially or, preferably, simultaneously. The active ingredients together with other additives are advantageously pre-formulated as a single mixture. It should be emphasised that fludioxonil and fluazinam 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.

Fludioxonil and fluazinam 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.

Use rates for the composition of the invention vary within the range from about 5 gai/Ha to about 2,500 gai/Ha, depending on the crop and the disease.

Preferably the use rates vary within the range from about 10 gai/Ha to about 1,500 gai/Ha.

Still more preferably the use rates vary within the range from about 20 gai/Ha to about 1,000 gai/Ha.

Still more preferably the use rates vary within the range from about 50 gai/Ha to about 1,000 gai/Ha. EXAMPLES It will be appreciated that the compositions are provided as non-limiting examples only and that other synergistic fungicidal compositions comprising fludioxonil and fluazinam as active ingredients will also fall within the ambit of the present invention.

EXAMPLE 1. Fludioxonil fluazinam SC Disperse 6 g VEEGUM (magnesium aluminium silicate) with high shear mixing into about 250 ml of water followed by a defoamer and a suitable dispersing agent comprising 20 g sodium polynaphthalene sulfonate and 10 g non-ionic wetting agent. Add 105 g technical grade fludioxonil and 129 g technical grade fluazinam, in turn, to the mixture with vigorous stirring. Pass the resulting fungicide mixture through a Dyno mill or similar bead mill at a rate that results in a particle size less than 5 pm. Disperse 2 g Xanthan gum in 200 ml water, then add the resulting gel to the fungicide mixture along with a preservative comprising 2.5 g 40% formaldehyde. Finally add water to make the volume up to 1000 mi. The resulting suspension concentrate comprises 100 g/L fludioxonil and 125 g/L fluazinam, and can be diluted with water ready for use.

EXAMPLE 2. Fludioxonil fluazinam WP Blend 386 g fluazinam tech, 330 g fludioxonil tech, 5 g sodium naphthalene sulfonate, and 20 g sodium polynaphthalene sulfonate, then make up to 1000 g with china clay. Air mill the resulting mixture to approximately 5 urn. The resulting wettable powder containing 300 g/kg fludioxonil and 375 g/kg fluazinam can be diluted with water ready for use.

EXAMPLE 3. Fludioxonil fluazinam EC Dissolve 102.5 g fludioxonil tech and 55 g fluazinam tech in 607.5 g Aromatic 150 and 75 g methyl pyrrolidone solvents. When fully dissolved add 75 g SOPROPHOR BSU and 75 g TENSIOFIX 8427, and stir to dissolve. The resulting emulsifiable concentrate formulation comprising 100 g/L fludioxonil and 50 g/L fluazinam may be diluted with water ready for use.

In the following example, the synergistic fungicidal effects of mixtures comprising fludioxonil and fluazinam as active ingredients are demonstrated in vitro. Synergy was determined by the "Wadley method" for similar joint action as disclosed 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: 1. ED(exp) = (a + <b)/(a/EDA + b/EDB), 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. 11 If SF > 1, there is synergistic interaction between the fungicides, if SF < 1, there is antagonistic interaction, and if SF = 1, there is additive action (i.e. similar joint action).

The end point used was ECgo, the concentration producing 90% inhibition of fungal growth. EC values were calculated by regression analysis of dose response data using the GraphPad Prism software.

EXAMPLE 4.

Botrytis cinerea Pers (Botrytiotiriia fuckliana (de Bary) Whetzel 1945) was grown on malt extract agar plates for 3 days at 25°C in the presence of fludioxonil alone (A), or fluazinam alone (B), and the mixtures shown in Table 1 ECgo(obs) ECgo(exp) SF Fludioxonil 8.430 3:1 Ratio 0.329 0.445 1.349 1:1 Ratio 0.135 0.228 1.686 1:3 Ratio 0.090 0.154 1.707 Fluazinam 0.116 Table 1. Synergy was observed at all three ratios.

The effectiveness of the synergistic fungicidal composition of the invention is demonstrated by control of Botrytis in wine grapes as shown in the following examples. Trials were performed using a randomized complete block design with four replicates. Individual plots were sized equally to provide at least 100 easily assessable bunches, and assessments were performed once botrytis became apparent towards the end of the season. Treatments were applied to each side of the plot to achieve full dilute coverage using a calibrated mist blower at full throttle with a spout end diffuser in place. All treatments included a non-ionic surfactant at 25 ml/100 L of spray mix. Treatments were applied to either the full canopy or the canopy zone containing grape bunches (bunch line), and water rates varied for each depending on canopy cover, crop maintenance, and bunch presence within the canopy. Data were analysed by ANOVA and means were compared using Duncan's Multiple Range Test (P = 0.05) using the Agricultural Research Manager software package (Gylling Data Management, Inc.). 12 EXAMPLE 5.

Table 2.

Trial 2404 Botrytis bunch rot (% incidence) Treatment Rate (gai/100 L) 14 DAV 21 DAV 28 DAV DAV 43 DAV 49 DAV Fludioxonil + Fluazinam + 24.5b 28.5b .0b 27.6b 28.1c .3b Full canopy Fluazinam 50 .5b 24.5b .5b 28.0b 38.3bc 44.8b Fludioxonil + Cyprodonil + 22.6b 26.0b 26.0b 27.0b 32.8bc 37.6b Fludioxonil + Fluazinam + .5b 21.5b .5b 22.0b .3bc 32.0b Bunch line Fluazinam 50 21.1b 19.0b .5b 34.0ab 42.8b 41.0b Fludioxonil + Cyprodonil + 29.7b 26.0b 26.5b 21.0b 32.3bc 38.0b Untreated 46.5a 43.0a 52.0a 44.0a 61.0a 62.9a LSD (P=0.05) .08 12.44 9.4 13.14 12.86 .98 Chardonnay grapes in a Hawkes Bay vineyard were sprayed with the composition of Example 1, alongside fluazinam alone and an industry standard comprising fludioxonil and the anilinopyrimidine fungicide cyprodonil. Fungicides were applied on three occasions corresponding to 80% capfall (1,000 L/Ha full canopy, 650 L/Ha bunch line), bunch closure (900 L/Ha full canopy, 650 L/Ha bunch line), and veraison (800 L/Ha full canopy, 450 L/Ha bunch line). Table 2 shows the mean % incidence (frequency of bunches showing any degree of rot) of bunch rot at various days after veraison (DAV). All treatments produced a significant reduction compared with untreated controls, either as a full canopy spray or as a bunch line spray at reduced water rates. The synergistic mixture of fludioxonil and fluazinam was numerically superior to the industry standard in the critical period approaching harvest, and contains a lower rate of total active ingredient.

EXAMPLE 6.

Table 3.

Trial 2409 Botrytis bunch rot (% area infection) Treatment Rate (gai/100 L) 16 DAV 29 DAV 36 DAV 42 DAV 49 DAV 57 DAV Full canopy Fludioxonil + Fluazinam + 0.4bc 0.3b 0.6c 1.0cd 1.0c 2.0b Fluazinam 50 0.6bc 0.3b 0.5c 0.7d 1.1c 1.0b Fludioxonil + Cyprodonil + 0.6bc 0.5b 2.1bc 2.9bc 4.3b 4.8b 13 Fludioxonil + Fluazinam + 0.4bc 0.2b 0.5c 0.8d 0.6c 1.5b Bunch line Fluazinam 50 0.8ab 0.5b 0.3c 0.6d 0.6c 1.4b Fludioxonil + Cyprodonil + 0.8abc 0.5b 3.8ab 3.4b 1.7c 4.3b Untreated 1.0a 1.9a .4a 6.7a 8.6a 8.5a LSD (P=0.05) 0.35 0.42 2.02 1.94 2.57 3.51 Semillon grapes in a Hawkes Bay vineyard were sprayed with the fungicides of Example 5 at 80% capfall (700 L/Ha full canopy, 480 L/Ha bunch line), bunch closure (1,100 L/Ha full canopy, 400 L/Ha bunch line), and veraison (750L/Ha full canopy, 350 L/Ha bunch line). Table 3 shows the mean % bunch area affected with botrytis rot at various days after veraison (DAV). All treatments produced a significant reduction compared with untreated controls, either as a full canopy spray or as a bunch line spray at reduced water rates. At all assessment times the synergistic composition of the invention comprising fludioxonil and fluazinam was numerically superior to the industry standard fungicide used in the trial.

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.

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.

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. 14 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 an improved fungicidal composition comprising components (A) fludioxonil and (B) fluazinam to achieve synergistic ratios of from about 20:1 to 1:20 and optionally (C) one or more biocides in separate containers or, as separate compartments, within the same container

Claims (19)

WHAT I/WE CLAIM IS: RECIEVED IPONZ 28 FEBRUARY 2012

1. A synergistic fungicidal composition comprising as active ingredients fludioxonil and fluazinam, characterised in that fludioxonil and fluazinam are present in synergisticaliy effective ratios from about 5:1 to about 1:5 by weight and whereby, in use, the composition is applied to plants, parts of plants, plant seeds or to soil at a rate ranging from 5 gai/Ha to about 2,500 gai/Ha based on the combined weights of fludioxonil and fluazinam.

2. The synergistic fungicidal composition according to claim 1 wherein the ratio of fludioxonil to fluazinam is from about 3:1 to about 1:3 by weight.

3. The synergistic fungicidal composition according to claim 1 or 2 containing 0.1 to 60% fludioxonil and 0.1% to 60% fluazinam on a weight/weight basis or a weight/volume basis.

4. The synergistic fungicidal composition according to any one of the preceding claims whereby the composition is applied at a rate ranging from 10 gai/Ha to about 1,500 gai/Ha.

5. The synergistic fungicidal composition according to any one of the preceding claims whereby the composition is applied at a rate ranging from 50 gai/Ha to about 1,000 gai/Ha.

6. The synergistic fungicidal composition according to any one of the preceding claims whereby the composition is formulated as a suspension concentrate, an emulsion, a granule, a powder or a capsule suspension.

7. The synergistic fungicidal composition according to any one of the preceding claims whereby the composition comprises an additional biocide including a fungicide, an insecticide, or a bactericide.

8. The synergistic fungicidal composition according to claim 7 whereby the additional biocide is an insecticide.

9. The synergistic fungicidal 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.

10. A method for controlling fungal diseases on plants or plant parts which comprises applying plants, parts of plants, seeds or to soil a fungicidally effective amount of a synergistic fungicidal composition according to any of the preceding claims characterised in that fludioxonil and fluazinam are present in synergisticaliy effective ratios from about 5:1 to about 1:5 by weight RECIEVED IPONZ 28 FEBRUARY 2012 and whereb the composition is applied to plants, parts of plants, plant seeds or to soil at a rate ranging from 5 gai/Ha to about 2,500 gai/Ha based on the combined weights of fludioxonil and fluazinam.

11. The method according to claim 10 wherein the ratio of fludioxonil to fluazinam is from about 3:1 to about 1:3 by weight.

12. The method according to claim 10 or 11 whereby the composition is applied at a rate ranging from 10 gai/Ha to about 1,500 gai/Ha.

13. The method according to any of claims 10 to 12 whereby the composition is applied at a rate ranging from 50 gai/Ha to about 1,000 gai/Ha.

14. The method according to any one of claims 10 to 13 whereby the composition is applied at any stage of the crop cycle excluding the withholding period.

15. The method according to any one of claims 10 to 14 whereby the composition is diluted with water before being applied to plants, parts of plants, seeds or to soil by conventional means including spraying, sprinkling, irrigating and coating.

16. The method according to any one of claims 10 to 15 whereby fludioxonil and fluazinam may be applied simultaneously or sequentially.

17. The method according to any one of claims 10 to 16 whereby fludioxonil and fluazinam may be tank mixed prior to application.

18. A synergistic fungicidal composition according to any one of claims 1 to 9 substantially as hereinbefore described with reference to any on of the accompanying examples.

19. A method for controlling fungal diseases on plants or plant parts according to any one of claims 10 to 17 substantially as hereinbefore described with reference to any of the accompanying examples. PIPERS, Patent Attorneys for Zelam Limited