WO2011124586A1

WO2011124586A1 - Post-harvest treatment method using a synergistic combination of fludioxonil and fenpropimorph

Info

Publication number: WO2011124586A1
Application number: PCT/EP2011/055314
Authority: WO
Inventors: Dany Leopold Jozefien Bylemans; Hans Bernhard Leithoff; Ana Carmen Diaz Marquina; Mark Arthur Josepha Van Der Flaas
Original assignee: Janssen Pharmaceutica Nv
Priority date: 2010-04-08
Filing date: 2011-04-06
Publication date: 2011-10-13

Abstract

The present invention relates to a post-harvest treatment method for the protection of harvested crops such as cereals, fruit, cutflowers or vegetables, against phytopathogenic fungi comprising applying to the harvested crops a composition comprising a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect.

Description

POST-HARVEST TREATMENT METHOD USING A SYNERGISTIC

COMBINATION OF FLUDIOXONIL AND FENPROPIMORPH

[0001] The present invention relates to a post-harvest treatment method for the protection of harvested crops such as cereals, fruit, cutflowers or vegetables, against phytopathogenic fungi comprising applying to the harvested crops a composition comprising a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect.

[0002] Antifungal compositions comprising fludioxonil, and use thereof for the protection of technical materials, have been described in WO-2005/051081 .

WO-2006/067390 discloses a method of treating building materials such as gypsum wallboards with a synergistic mixture comprising fludioxonil and another fungicide. WO-2008/131901 describes synergistic compositions containing either fenpropimorph or fludioxonil along with a further fungicide.

[0003] Post-harvest treatment of harvested crops against phytopathogenic fungi can prevent or reduce certain post-harvest storage disorders such as e.g. scald, scorch, softening, senescent breakdown, lenticel spots, bitter pit, browning, water core, vascular breakdown and the like.

[0004] It has now been found that the combination of fludioxonil, or a salt thereof, (hereinafter referred to as component I) and fenpropimorph, or a salt thereof,

(hereinafter referred to as a component II), has a synergistic fungicidal effect when used in a post-harvest treatment method for the protection of harvested crops against phytopathogenic fungi comprising applying to the harvested crops a composition comprising said combination.

[0005] Fludioxonil, component (I), is employed as an agricultural fungicide to control phytopathogenic fungi such as Botrytis cmerea. It is the generic name of the compound 4-(2,2-difluoro-1 ,3-benzodioxol-4-yl)-1 H-pyrrole-3-carbonitrile, which compound is represented by the formula

[0006] Fenpropimorph, component (II), is a systemic fungicide for use in the protection of cereals. It is the generic name of the compound cis-4-[3-(4-ie f-butyl- phenyl)-2-methylpropyl]-2,6-dimethylmorpholine which compound is represented by the formula

[0007] The components (I), i.e. fludioxonil or a salt thereof, and component (II), i.e. fenpropimorph or a salt thereof, may be present in their free base form or in the form of an acid addition salt, the latter being obtained by reaction of the base form with an appropriate acid. Appropriate acids comprise, for example, inorganic acids, such as the hydrohalic acids, i.e. hydrofluoric, hydrochloric, hydrobromic and hydroiodic, sulfuric acid, nitric acid, phosphoric acid, phosphinic acid and the like; or organic acids, such as, for example, acetic, propanoic, hydroxyacetic, 2-hydroxypropanoic,

2-oxopropanoic, ethanedioic, propanedioic, butanedioic, (Z)-2-butenedioic, (E)-2- butenedioic, 2-hydroxybutanedioic, 2,3-dihydroxy-butanedioic, 2-hydroxy-1 ,2,3- propanetricarboxylic, methanesulfonic, ethanesulfonic, benzenesulfonic, 4-methyl- benzenesulfonic, cyclohexanesulfamic, 2-hydroxybenzoic, 4-amino-2-hydroxy-benzoic and the like acids.

[0008] The components (I) and (II) for use in the post-harvest treatment method according to the present invention should preferably be present in a substantially pure form, i.e. free from chemical impurities (such as co-products or residual solvents) resulting from their manufacturing and/or handling processes in view to safely control the phytopathogenic fungi management programs for which they are intended. The term "substantially pure" as used hereinbefore means a purity (either chemical or optical), as determined by methods conventional in the art such as high performance liquid chromatography or optical methods, of at least about 96%, preferably at least 98% and more preferably at least 99%.

[0009] The compositions of the present invention are active against a broad range of phytophatogenic fungi. As examples of such fungi there may be named Colletotrichum spp., e.g. Colletotrichum musae, Colletotrichum gloeosporioides, Colletotrichum coccodes; Fusarium spp., e.g. Fusarium semitectum, Fusarium moniliforme, Fusarium solani, Fusarium oxysporum; Verticillium spp., e.g. Verticillium theobromae; Nigrospora spp.; Botrytis spp., e.g. Botrytis cmerea; Geotrichum spp., e.g. Geotrichum candidum; Phomopsis spp., Phomopsis natalensis; Diplodia spp., e.g. Diplodia citri;

Alternaria spp., e.g. Alternaria citri, Alternaria alternata; Phytophthora spp., e.g.

Phytophthora citrophthora, Phytophthora fragariae, Phytophthora cactorum,

Phytophthora parasitica; Septoria spp., e.g. Septoria depressa; Mucor spp., e.g. Mucor piriformis; Monilinia spp., e.g. Monilinia fructigena, Monilinia laxa; Venturia spp., e.g.

Venturia inaequalis, Venturia pyrina; Rhizopus spp., e.g. Rhizopus stolonifer,

Rhizopus oryzae; Glomere Ha spp., e.g. Glomerella cingulata; Sclerotinia spp., e.g.

Sclerotinia fruiticola; Ceratocystis spp., e.g. Ceratocystis paradoxa; Penicillium spp., e.g. Penicillium funiculosum, Penicillium expansum, Penicillium digitatum, Penicillium italicum; Gloeosporium spp., e.g. Gloeosporium album, Gloeosporium perennans,

Gloeosporium fructigenum, Gloeosporium singulata; Phlyctaena spp., e.g. Phlyctaena vagabunda; Cylindrocarpon spp., e.g. Cylindrocarpon mali; Stemphyllium spp., e.g.

Stemphyllium vesicarium; Phacydiopycnis spp., e.g. Phacydiopycnis malirum;

Thielaviopsis spp., e.g. Thielaviopsis paradoxy; Aspergillus spp., e.g. Aspergillus niger, Aspergillus carbonarius; Nectria spp., e.g. Nectria galligena; Pezicula spp..

[0010] As examples of the wide variety of harvested crops that can be protected according to the post-harvest treatment method of the present invention are in general cereals, fruit, cutflowers or vegetables. More specifically there may be named for example cereals, e.g. wheat, barley, rye, oats, rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pome and stone fruit and berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries;

leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginous plants, e.g. rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa, ground-nuts;

cucurbitaceae, e.g. pumpkins, gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton, flax, hemp, jute; citrus fruit, e.g. orange, lemon, grapefruit, mandarin;

vegetables, e.g. spinach, lettuce, asparagus, brassicaceae such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado, cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee, sugar-cane, tea, vines, hops, bananas, rubber plants, as well as ornamental plants, e.g. flowers, shrubs, deciduous trees and evergreen trees such as conifers. This enumeration of culture plants is given with the purpose of illustrating the invention and not to delimiting it thereto.

[0011] A particular post-harvest treatment method of the present invention if the post-harvest treatment of fruit, especially citrus fruit. In the latter instance, the fruit will be sprayed with or dipped or drenched into a liquid formulation or the fruit may be coated with a waxy composition. The latter waxy composition conveniently is prepared by thoroughly mixing a suspension concentrate with a suitable wax. The formulations for spray, dip or drench applications may be prepared upon dilution of a concentrate such as, e.g. an emulsifiable concentrate, a suspension concentrate or a soluble liquid, with an aqueous medium. Such concentrate in most instances consists of the active ingredients, a dispersing or suspending agent (surfactant), a thickening agent, a small amount of organic solvent, a wetting agent, optionally some anti-freeze agent, and water.

[0012] The relative proportions of component (I) and components(ll) in the embodied compositions are those proportions which result in unexpected synergistic efficacy against fungi, especially against plant, fruit and seed pathogens, when compared to a composition including, as an active ingredient, either component (I) alone or component (II) alone. As will readily be understood by those skilled in the art, the said synergistic efficacy may be obtained within various proportions of components (I) and (II) in the composition, depending on the kind of fungi towards which efficacy is measured and the substrate to be treated. Based on the teachings of the present application, determination of the synergistic effect of such combinations can be performed according to the procedures of the Poison Plate Assay as described in Experiment 1 . As a general rule, it may be said that for most phytopathogenic fungi the suitable proportions by weight of the amount of component (I) to component (II) in the fungicidal compositions should lie in the range from 10:1 to 1 :10. Particularly, this range is from 4:1 to 1 :4, more particularly from 3:1 to 1 :3 or 2:1 to 1 :2.

[0013] The quantity of each of the active ingredients, i.e. component (I) or component (II), in the compositions for use in the post-harvest treatment method according to the present invention will be so that a synergistic fungicidal effect is obtained. It is contemplated that the ready to use compositions for use in said post- harvest treatment method comprise component (I) and component (II) in a range from 10 to 1.000 mg/l.

[0014] Furthermore the compositions for use in the post-harvest treatment method according to the present invention comprise a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect, also comprise one or more acceptable carriers. [0015] In an embodiment, the present invention also relates to a post-harvest treatment method for the protection of harvested crops against phytopathogenic fungi comprising applying to the harvested crops a composition containing a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect; and one or more carriers. As a general rule, it may be said that for most phytopathogenic fungi the suitable proportions by weight of the amount of component (I) to component (II) in the fungicidal compositions should lie in the range from 10:1 to 1 :10. Particularly, this range is from 4:1 to 1 :4, more particularly from 3:1 to 1 :3 or 2:1 to 1 :2.

[0016] The carriers are any material or substance with which the composition of components (I) and (II) is formulated in order to facilitate its application/dissemination to the harvested crop to be treated, for instance by dissolving, dispersing, or diffusing the said composition, and/or to facilitate its storage, transport or handling without impairing its antifungal effectiveness. Said acceptable carriers may be a solid or a liquid or a gas which has been compressed to form a liquid, i.e. the compositions of this invention can suitably be used as concentrates, emulsions, emulsifiable concentrates, oil miscible suspension concentrates, oil-miscible liquid, soluble concentrates, solutions, granulates, dusts, sprays, aerosols, pellets, or powders.

[0017] In many instances the fungicidal compositions to be used directly can be obtained from concentrates, such as e.g. emulsifiable concentrates, suspension concentrates, or soluble concentrates, upon dilution with aqueous or organic media, such concentrates being intended to be covered by the term composition as used in the definitions of the present invention. Such concentrates can be diluted to a ready to use mixture in a spray tank shortly before use. Preferably the compositions of the invention should contain from about 0.01 to 95% by weight of the combination of components (I) and (II). More preferably this range is from 0.1 to 90% by weight. Most preferably this range is from 1 to 80% by weight, depending on the type of formulation to be selected for specific application purposes, as further explained in details hereinafter. [0018] An emulsifiable concentrate is a liquid, homogeneous formulation of the components (I) and (II) to be applied as an emulsion after dilution in water.

A suspension concentrate is a stable suspension of the active ingredients in a fluid intended for dilution with water before use. A soluble concentrate is a liquid, homogeneous formulation to be applied as a true solution of the active ingredients after dilution in water. [0019] Apart from both the aforementioned components (I) and (II), the compositions according to the present invention may further comprise other active ingredients, e.g. other microbiocides, in particular fungicides, and also insecticides, acaricides, nematicides, herbicides and plant growth regulators. [0020] The components (I) and (II) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. They are therefore formulated following art-known procedures to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomizing, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

[0021] The formulations, i.e. the compositions, preparations or mixtures comprising the active ingredients and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants). [0022] Suitable solvents are aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. dimethylbenzene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic or alicyclic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N- methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water. [0023] The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated absorbent carriers are of the porous type, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

[0024] Suitable surface-active compounds to be used in the compositions of the present invention are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

[0025] Appropriate carriers and adjuvants for use in the compositions of the present invention may be solid or liquid and correspond to suitable substances known in the art for preparing formulations for treating plants or the loci thereof, or for treating plant products, in particular for treating wood, such as, for example, natural or regenerated mineral substances, solvents, dispersants, surfactants, wetting agents, adhesives, thickeners, binders, fertilizers, anti-freeze agents, repellents, colour additives, corrosion inhibitors, water-repelling agents, siccatives, UV-stabilizers and other active ingredients. [0026] Suitable anionic surfactants can be both water-soluble soaps and water- soluble synthetic surface-active compounds.

[0027] Suitable soaps are the alkali metal salts, earth alkaline metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22 e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. In addition, there may also be mentioned fatty acid methyltaurin salts.

[0028] More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or

alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, earth alkaline metal salts or unsubstituted or substituted ammonium salts and contain an alkyl radical having from 8 to 22 carbon atoms said alkyl also comprising radicals derived from acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzene sulfonic acid,

dibutylnaphthalene-sulfonic acid, or of a naphthalene-sulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.

[0029] Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. [0030] Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopoly- propylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

[0031] Representative examples of non-ionic surfactants are nonylpheno-lpolyethoxy ethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxy- ethanol. Fatty acid esters of polyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

[0032] The compositions comprising a combination of fludioxonil (I) and

fenpropimorph (II) whereby (I) and (II) are in respective proportions to provide a synergistic fungicidal effect can be applied in the post-harvest treatment method for the protection of harvested crops against phytopathogenic fungi by dipping, drenching, dump tank, spraying, fogging, brushing, coating, waxing wax and electrostatic application.

[0033] In an embodiment, the present invention also relates to the use of a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect for post-harvest treatment to protect harvested crops against phytopathogenic fungi. [0034] Experimental part

Experiment 1 : Poison plate assay

Activity against fungal growth was determined with the poison plate assay.

Test models : Fungi : to each well of a 24-well microtiter plate, 1000 μΙ of a rich

(Potato Dextrose Agar, PDA: 4g potato infusion, 20g bacto dextrose and 15g bacto agar in I liter deionised water) or poor (Glucose Agar, GA: 10g glucose, 1 .5g K₂HP0₄, 2g KH₂P0₄, 1 g (NH₄)₂S0₄, 0.5g MgS0₄ and 12.5g agar in 1 liter deionised water) medium containing the appropriate combination of the test compounds in one of the concentrations of a dose series is added. The nutrient medium is inoculated with the test fungi by adding a spore/mycelium suspension (10 μΙ) or a small piece of agar from the margin of an actively growing colony and incubated under dark at 27°C with 70 % relative humidity. The growth of the fungi is evaluated after two weeks.

Glucose agar was used in some experiments instead of PDA (Potato Dextrose Agar), as an alternative, poorer medium for the fungi, in order to increase the chances of detecting activity in compounds whose mode of action might be partly circumvented by fungi on a richer medium.

Concentrations: a 24-step doses series is applied, each step being 0.75 times the concentration of the previous step, as follows : 25.00 - 18.75 - ....0.04 - 0.03 ppm

% product A + % product B

100 + 0

80 + 20

66 + 33

50 + 50

33 + 66

20 + 80

0 + 100

Test species: Fungi :

Botrytis cinerea BC03019 (PDA medium)

Colletotrichum musae MUCL nr2 (glucose agar medium) MIC values (minimum inhibitory concentration in ppm total active ingredient) were noted and synergy was calculated using the Synergy Index method described by Kull et al. (Kull, F.C., P.C. Eismann, H.D. Sylvestrowicz, and R.L. Mayer (1961 ) "Mixtures of quaternary ammonium compounds and long-chain fatty acids as antifungal agents" Applied Microbiology 9: 538-541 ; also see Zwart Voorspuij, A.J., and C.A.G. Nass (1957) "Some aspects of the notions additivity, synergism and antagonism in the simultaneous activity of two antibacterial agents in vitro" Arch, intern.

Pharmacodynamie 109: 21 1 -228; Steinberg, D.C. (2000) "Measuring synergy" cosmetics & Toiletries 1 15(1 1 ): 59-62; and Lada, A., A.N. Petrocci, H.A. Green, and J.J. Merianos (1977) "Antimicrobial composition" US Patent 4061750, 3pp.) :

Synergy Index (SI) =

wherein:

• Q_A is the concentration of compound A in ppm, acting alone, which produced an end point (e.g. MIC),

· Q_a is the concentration of compound A in ppm, in the mixture, which produced an end point (e.g. MIC),

• Q_B is the concentration of compound B in ppm, acting alone, which produced an end point (e.g. MIC),

• Qe is the concentration of compound B in ppm, in the mixture, which produced an end point (e.g. MIC).

When the Synergy Index is greater than 1 .0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1 .0, synergism is demonstrated.

MIC-values (minimum inhibitory concentration in ppm) and synergy index of fludioxonil, i.e. component (I), and fenpropimorph, i.e. component (II), and their combination against Botrytis cinerea

Combination ratio (I) to (II) MIC-values in synergy

ppm index

100 + 0 0.1 1 -

80 + 20 0.1 1 0.82

66 + 33 0.14 0.89

50 + 50 0.14 0.70

33 + 66 0.25 0.91

20 + 80 0.33 0.85

0 + 100 1 .06 - MIC-values (minimum inhibitory concentration in ppm) and synergy index of fludioxonil, i.e. component (I), and fenpropimorph, i.e. component (II), and their combination against Colletotrichum musae

Combination ratio (I) to (II) MIC-values in synergy

ppm index

100 + 0 33.33 -

80 + 20 5.93 0.23

66 + 33 4.45 0.20

50 + 50 4.45 0.23

33 + 66 4.45 0.26

20 + 80 4.45 0.28

0 + 100 14.06 -

Claims

1 . A post-harvest treatment method for the protection of harvested crops against phytopathogenic fungi comprising applying to the harvested crops a composition comprising a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect.

2. The method as claimed in claim 1 wherein the ratio by weight of component (I) to component (II) is 10:1 to 1 :10.

3. The method as claimed in claim 2 wherein the ratio by weight of component (I) to component (II) is 4:1 to 1 :4.

4. The method as claimed in claim 3 wherein the ratio by weight of component (I) to component (II) is 3:1 to 1 :3.

5. The method as claimed in any one of claims 1 to 4 wherein the harvested crops are cereals, fruit, cutflowers or vegetables.

6. The method as claimed in claim 6 wherein the harvested crop is fruit.

The method as claimed in any one of claims 1 to 6 wherein the composition comprising component (I) and component (II) is a concentrate, emulsion, emulsifiable concentrate, oil miscible suspension concentrate, oil-miscible liquid, soluble concentrate, solution, granulate, dust, spray, aerosol, pellet, or powder.

The method as claimed in any one of claims 1 to 6 wherein the composition is a ready to use composition or a concentrated formulation that has to be diluted before use.

The method as claimed in any one of claims 1 to 6 wherein the composition is applied by dipping, drenching, dump tank, spraying, fogging, brushing, coating, waxing wax and electrostatic application.

10. Use of a combination of fludioxonil, or a salt thereof, as a component (I) and fenpropimorph, or a salt thereof, as a component (II) whereby component (I) and component (II) are in respective proportions to provide a synergistic fungicidal effect for post-harvest treatment to protect harvested crops against phytopathogenic fungi.

1 1 . The use as claimed in claim 10 wherein the ratio by weight of component (I) to component (II) is 10:1 to 1 :10.

12. The use as claimed in claim 1 1 wherein the ratio by weight of component (I) to component (II) is 4:1 to 1 :4.

13. The use as claimed in claim 12 wherein the ratio by weight of component (I) to component (II) is 3:1 to 1 :3.