Paraffinic Oil-In-Water Emulsions for Controlling Infection of Crop Plants by Fungal Pathogens

(19) TZZ _¥_T

(11) EP 2 713 749 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: A01N 27/00 (2006.01) A01N 25/04 (2006.01) 22.05.2019 Bulletin 2019/21 A01N 37/50 (2006.01) A01N 43/54 (2006.01) A01N 43/653 (2006.01) A01N 47/24 (2006.01) (2006.01) (2006.01) (21) Application number: 12793919.7 A01P 3/00 A01N 43/40 A01N 43/50 (2006.01) A01N 43/60 (2006.01) A01N 43/76 (2006.01) A01N 43/88 (2006.01) (22) Date of filing: 04.06.2012 A01N 47/14 (2006.01) A01N 47/38 (2006.01) A01N 55/00 (2006.01)

(86) International application number: PCT/CA2012/050376

(87) International publication number: WO 2012/162846 (06.12.2012 Gazette 2012/49)

(54) PARAFFINIC OIL-IN-WATER EMULSIONS FOR CONTROLLING INFECTION OF CROP PLANTS BY FUNGAL PATHOGENS PARAFFINISCHE ÖL-IN-WASSER-EMULSIONEN ZUR STEUERUNG DER INFEKTION VON ZUCHTPFLANZEN DURCH PATHOGENE PILZE ÉMULSIONS HUILE PARAFFINIQUE DANS EAU UTILISABLES EN VUE DE LA LUTTE CONTRE LES INFECTIONS PAR DES CHAMPIGNONS PATHOGÈNES CHEZ LES PLANTES CULTIVÉES

(84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB EP-A2- 0 267 778 WO-A1-2009/155693 GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO WO-A1-2009/155693 WO-A2-2012/040804 PL PT RO RS SE SI SK SM TR CA-A1- 2 507 482 US-A- 4 041 164 US-A- 5 393 770 (30) Priority: 03.06.2011 US 201161493118 P 13.06.2011 US 201161496500 P • G C Schutte ET AL: "Application of azoxystrobin for control of benomyl-resistant Guignardia (43) Date of publication of application: citricarpa on ’Valencia’ oranges in South Africa", 09.04.2014 Bulletin 2014/15 Plant Disease, 1 July 2003 (2003-07-01), page 784, XP055138019, St. Paul Retrieved from the (73) Proprietor: Suncor Energy Inc. Internet: Calgary, Alberta T2P 3E3 (CA) URL:http://search.proquest.com/docview/229 879498 [retrieved on 2014-09-29] (72) Inventors: • Janna Beckerman: "Disease Management • FEFER, Michael Strategies for Horticultural Crops Using organic Whitby, Ontario L1N 7A7 (CA) Fungicides", Purdue Extension, 1 April 2008 •LIU,Jun (2008-04-01), pages 1-4, XP055143138, Retrieved Oakville, Ontario L6H 6H3 (CA) from the Internet: URL:https://www.extension.purdue.edu/extme (74) Representative: Peterreins Schley dia/bp/bp-69-w.pdf [retrieved on 2014-09-29] Patent- und Rechtsanwälte Hermann-Sack-Strasse 3 80331 München (DE)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 713 749 B1

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• "SUNSPRAY 6E - Material Safety Data Sheet", , 1 • SCHUTTE, G.C. ET AL.: ’Application of June 2009 (2009-06-01), pages 1-5, XP055143573, azoxystrobin for control of benomyl-resistant Retrieved from the Internet: Guignardia citricarpa on ’Valencia’ oranges in URL:http://www.recarroll.com/cw3/Assets/pr South Africa’ PLANT DISEASE vol. 87, no. 7, 01 oduct_files/Sunspray 6E.pdf [retrieved on July 2003, pages 784 - 788, XP055138019 2014-09-30] • SOOMARY, S.D. ET AL.: ’Evaluation of Remarks: Fungicides for Control of the Leaf Spot Disease Thefile contains technical information submitted after Caused by Mycosphaerella eumusae on Banana the application was filed and not included in this in Mauritius’ FOOD AND AGRICULTURAL specification RESEARCH COUNCIL, PROCEEDINGS FOURTH ANNUAL MEETING OF AGRICULTURAL SCIENTISTS February 2001, pages 61 - 65, XP008171895 • DELL, K.J. ET AL.: ’The efficacy of JMS Sylet-Oil on grape powdery mildew and Botrytis bunch rot and effects on fermentation’ AMERICAN JOURNAL OF ENOLOY AND VITICULTURE vol. 49, no. 1, 1998, pages 11 - 16, XP055138346

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Description

TECHNICAL FIELD

5 [0001] The present invention relates to the use of a fungicidal composition comprising: a paraffinic oil, an emulsifier, a copper phthalocyanine pigment and a silicone surfactant and wherein:the ratio of the paraffinic oil to the pigment is from about 5:1 to 100:1; the weight ratio of the paraffinic oil to the emulsifier is from 10:1 to 500:1; and the weight ratio of the pigment to the silicone surfactant is from 2:1 to 50:1, for controlling infection of a crop plant by a fungal pathogens. Also disclosed are combinations containing a paraffinic oil and one or more of the following: one or more emulsifiers, 10 one or more pigments, one or more silicone surfactants, one or more anti-settling agents, one or more conventional chemical fungicides (e.g., a DMI or a QoI), and water. In some implementations, the combinations can be in the form of a single composition (e.g., which is contained within a storage pack or a vessel (e.g., a tank) suitable for applying the composition to a plant, e.g., crop plant). Typically, the composition is applied to a plant after dilution with water. In other implementations, the combinations can include two or more separately contained (e.g., packaged) compositions, each 15 containing one or more of the above-mentioned components. Said compositions can be combined and applied to a plant typically after dilution with water; or each composition can be applied separately to the same plant either simultaneously or sequentially, and typically after dilution with water. This disclosure also features methods of using the combinations for controlling infection of a vascular crop plant by a fungal pathogen as well as methods of formulating combinations that include both oil and water as oil-in-water (O/W) emulsions. 20 BACKGROUND

[0002] Rusts are plant diseases caused by fungal pathogens of the order Pucciniales. Rusts can affect a variety of plants, including monocotyledons and dicotyledons, as well as various plant organs, including leaves, stems, fruits and 25 seeds. Rust is typically observed as colored powdery pustules composed off tiny spores that form on the lower plant organ surfaces. Common rust-causing fungal species include Gymnosporangium juniperi-virginianae (Cedar-apple rust) which attacks apple and pear and hawthorn; Cronartium ribicola (White pine blister rust); which attacks white pines and currants; Hemileia vastatrix (Coffee rust) which attacks coffee plant; Puccinia graminis (wheat stem rust) which attacks Kentucky bluegrass, barley, and wheat; Puccinia coronata (Crown Rust of Oats and Ryegrass) which attacks oats; 30 Phakopsora meibomiae and P. pachyrhizi (soybean rust) which attacks soybean and various legumes; Uromyces phaseoli (Bean rust) which attacks bean; Puccinia hemerocallidis (Daylily rust) which attacks Daylily; Puccinia persistens subsp. triticina causes (wheat rust in grains, also known as ’brown or red rust’); P. sriiformis (yellow or stripe rust); Uromyces appendeculatus which attacks bean. [0003] Wheat stem rust is caused by the fungus Puccinia graminis and is a significant disease affecting cereal crops, 35 particularly wheat (Triticum spp.) An epidemic of stem rust on wheat caused by race Ug99 is currently spreading across Africa, the Middle East, and Asia, and threatening large numbers of people who are dependent on wheat for sustenance. The rust fungus attacks the parts of the plant which are above ground. Spores that land on green wheat plants form a pustule that invades the outer layers of the stalk. Where infection has occurred on the stem or leaf, elliptical blisters or pustules called uredia develop. Infected plants produce fewer tillers and set fewer seed. 40 [0004] Soybean rust is a disease that primarily affects soybeans and other legumes. It is caused by two species of fungi, Phakopsora pachyrhizi and Phakopsora meibomiae. Soybean rust has been reported in Asia, Australia, Africa, South America and North America. Soybean rust is spread by wind-borne spores, which are released in cycles of seven days to two weeks. Yield losses can be severe with this disease and losses of 10-80% have been reported. [0005] Multi-pronged approaches are desirable to address the spread of fungal infection. A variety of preventative 45 methods may be employed. For example, rust diseases are correlated to relatively high moisture. Accordingly, avoidance of overhead watering at night, using drip irrigation, reducing crop density, and the use of fans to circulate air flow may serve to lower the relative moisture and decrease the severity of rust infection. [0006] Other strategies may include reducing the area of the plant that the pathogen destroys, or slowing down the spread of the fungus. Fungus-resistant plants may be used to interrupt the disease cycle because many rusts are host- 50 specific. This approach has proven very successful in the past for control of wheat stem rust; however, Ug99 is currently virulent against most wheat varieties. Currently, there are no commercial soybean varieties with resistance to soybean rust. Accordingly, soybean rust is managed with fungicides. [0007] In large agricultural operations, conventional synthetic fungicides can be used to control fungal pathogens. De- methylation inibitors (DMI) such tebuconazole (Folicur™, Bayer) and propioconazole (Tilt™) may be effective for the 55 control of wheat stem rust, while tetraconazole (Domark™, Valent) be effective for the control of soybean rust. Quinone Outside Inhibitors (QoI), such as pyraclostrobin (Headline™, BASF), may be effective for the control of soybean rust, while azoxystrobin (Quadris™) may be effective for the control of wheat stem rust. [0008] Conventional fungicides are generally applied by air to the foliage as contact between the pathogen with the

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fungicide is required for efficacy. This process can expensive and fungicide application is often reserved for seasons when foliar diseases are severe. Second, conventional fungicides typically target specific sites of important pathogen proteins. Accordingly, strains may develop resistance to the fungicide after repeat applications. Third, the efficacy of conventional chemical fungicides is not always satisfactory for some of the diseases, such as Fusarium Head Blight 5 (Scab). Finally, conventional fungicides are generally not acceptable for use in organic farming. [0009] As an alternative approach to conventional chemical fungicides, oil-in-water emulsions comprising paraffinic oils (paraffinic oil-in-water emulsions) and paraffinic spray oils have been used in turfgrass management practices for controlling turfgrass pests (see, for example, Canadian Patent Application 2,472,806 and Canadian Patent Application 2,507,482). In addition, oil-in-water formulations comprising paraffinic oils and a pigment for controlling turfgrass pests 10 have been reported (see, for example, WO 2009/155693). For example, Petro-Canada produces CIVITAS™, is a paraffinic oil-in-water emulsion that functions as a broad spectrum fungicide and insecticide for use on golf course turf and landscape ornamentals, used for example to control powdery mildew, adelgids and webworms on landscape ornamentals (US EPA REG. NO. 69526-13). Product labeling indicates that CIVITAS™ may be applied as part of an alternating spray program or in tank mixes with other turf and ornamental protection products; and that CIVITAS™ may be used as a 15 preventative treatment with curative properties for the control of many important diseases on turf, including fairways and roughs. [0010] WO 2009/155693 A1 discloses oil-in-water fungicidal formulations having pigment dispersed therein, the pigment being stable within the oil-in-water emulsion as a result of the addition of suitable silicone surfactants and suitable emulsifiers. 20 [0011] The article "Application of azoxystrobin for control of benomyl-resistant Guignardia citricarpa on ’Valencia’ oranges in South Africa", Plant Disease, 2003, page 784, by Schutte et al relates to the application of azoxystrobin on oranges. [0012] US 5 393 770 A discloses fungicidal compositions for foliar spray applications against fungi which are pathogenic to cereal crops. 25 [0013] US 4 041 164 A discloses fungicidal dispersions comprising a carboxylic acid amide, other than pyracarbolide, as the fungicidally-active ingredient and an aluminum chelate of a polynuclear hydroxy-quinone as a crystal growth stabilizer, dispersed in a paraffinic mineral oil, a liquid triglyceride, or a liquid ester. [0014] WO 2012/040804 A2 discloses an agrochemically synergistic formulation of triazoles, strobilurins and benz- imidazoles, in specific propotions for controlling and/or combating plagues and diseases caused therefrom in vegetable 30 cultures. [0015] EP 0 267 778 A2 discloses azole derivatives useful as fungicides and as plant growth regulators. [0016] The Material Safety Data Sheet "SUNSPRAY 6E", 2009, pages 1-5, discloses the ingredients of SUNSPRAY 6E.

SUMMARY 35 [0017] The present invention relates to the use of a fungicidal composition comprising a paraffinic oil-in-water emulsion, the paraffinic oil-in-water emulsion comprising a paraffinic oil, an emulsifier, a pigment and a silicone surfactant, for controlling infection of a crop plant by a fungal pathogen, wherein the pigment is a copper phthalocyanine and wherein the ratio of the paraffinic oil to the pigment is from about 5:1 to 100:1; the weight ratio of the paraffinic oil to the emulsi fier 40 is from 10:1 to 500: 1; and the weight ratio of the pigment to the silicone surfactant is from 2:1 to 50. [0018] The disclosure features combinations that include a paraffinic oil. The combinations includes one or more emulsifiers, one or more pigments, one or more silicone surfactants, optionally one or more anti-settling agents, optionally one or more conventional chemical fungicides (e.g., a DMI or a QoI), and water. In some implementations, the combinations can be in the form of a single composition (e.g., which is contained within a storage pack or a vessel (e.g., a 45 tank) suitable for applying the composition to a plant, e.g., crop plant). Typically, the composition is applied to a plant after dilution with water. In other implementations, the combinations can include two or more separately contained (e.g., packaged) compositions, each containing one or more of the above-mentioned components. Said compositions can be combined and applied to a plant typically after dilution with water; or each composition can be applied separately to the same plant either simultaneously or sequentially, and typically after dilution with water. This disclosure also features 50 methods of using the combinations for controlling infection of a vascular crop plant by a fungal pathogen as well as methods of formulating combinations that include both oil and water as oil-in-water (O/W) emulsions. [0019] It has been found that the combinations described herein (e.g., combinations that include one or more conventional chemical fungicides, such as a DeMethylation Inhibitor (DMI) or a Quinone outside Inhibitor (QoI) fungicide, and the components present in CIVITAS™/CIVITAS HARMONIZER™) are surprisingly effective in controlling fungal dis- 55 eases, including, e.g., wheat stem rust, soybean rust, leaf rust, stripe rust, fusarium head blight, spot blotch, and Septoria complex in vascular crop plants. [0020] In one aspect, uses are provided for combinations (e.g., fungicidal compositions) that include a paraffinic oil- in-water emulsion according to the invention in controlling infection of a vascular plant by a fungal pathogen.

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[0021] The plant is a crop plant. [0022] The plant may be monocotyledonous. The monocotyledonous plant may be of the order Poaceae. The plant may be of the genus Triticum, Secale, Hordeum, Oryza, Zea, or Elymus. The fungal pathogen may be of the order Pucciniales. The fungal pathogen may be of the genus Puccinia. The fungal pathogen may be of the species Puccinia 5 graminis, Puccinia triticina, or Puccinia sriiformis. The fungal pathogen can also be Bipolaris sorokiniana or Fusarium graminearum. [0023] The plant can be dicotyledonous. The plant can be of the order Fabaceae. The plant can be of the species Glycine max. The fungal pathogen can be of the genus Phakopsora. The fungal pathogen can be Phakopsora pachyrhizi andPhakopsora meibomiae. The plant canbe ofthe genusGossypium. The fungal pathogencan be Phakopsora gossypii. 10 [0024] The paraffinic oil can include a paraffin having a number of carbon atoms of from 12 to 50. The paraffin can have a number of carbon atoms of from about 16 to 35. The paraffin can have an average number of carbon atoms of 23. [0025] The paraffinic oil may have a paraffin content of at least 80%. The paraffinic oil may have a paraffin content of at least 90%. The paraffinic oil may have a paraffin content of at least 99%. [0026] The paraffinic oil can be used in a range from 0.9 to 233.6 L/Ha (13 to 3200 oz/acre) (i.e. 3 to 750 ml/100 square 15 meter (0.3 to 75 oz/1000 square feet)). The paraffinic oil can be used in a range from 2.9 to 46.7 L/Ha (40 to about 640 oz/acre). The oil-in-water emulsion can be used in a range from 18.7 to 467 L/Ha (2 to 50 gallons per acre) for foliar application. The oil-in-water emulsion can be used in a range from 1868 to 3736 L/Ha (200 to 400 gallons per acre) for soil drench application or water-in application with irrigation. [0027] The combinations (e.g., fungicidal compositions) can further include a de-methylation inhibitor (DMI). The DMI 20 may be tetraconazole, tebuconazole, propioconazole, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, prothioconazole, simeconazole, triadimefon, triadimenol, triticonazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenarimol, nuarimol, triforine, or pyrifenox. The DMI can be tebuconazole, and may be used in a range from about 0.022 to 0.56 kg ai./Ha (0.02 to 25 about 0.5 lb. ai./acre). The DMI may be propioconazole, and can be used in a range from about 0.011 to 0.7 kg ai./Ha (0.01 to about 0.6 lb. ai./acre). The DMI can be tetraconazole, and may be used in a range from 0.017 to 0.17 kg ai./Ha (0.015 to 0.15 lb. ai./acre). The DMI can be prothioconazole, and may be used in a range from 0.017 to 0.17 kg ai./Ha (0.02 to 0.4 lb. ai./acre). [0028] The combinations (e.g., fungicidal compositions) can further include a Quinone outside Inhibitor (QoI). The QoI 30 may be azoxystrobin, enestrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, dimoxystrobin, metominostrobin, orysastrobin, famoxadonem, fluoxastrobin, fenamidone, or pyribencarb. The QoI can be azoxystrobin, and may be used in a range from 0.011 to 0.56 kg ai./Ha (0.01 to 0.50 lb. ai./acre). The QoI can be pyraclostrobin, and may be used in a range from 0.022 to 0.40 kg ai./Ha (0.02 to 0.40 lb. ai./acre). [0029] The combinations (e.g., fungicidal compositions) include an emulsifier (e.g., a natural or synthetic alcohol 35 ethoxylate, an alcohol alkoxylate, an alkyl polysaccharide, a glycerol oleate, a polyoxyethylene-polyoxypropylene block copolymer, an alkyl phenol ethoxylate, a polymeric surfactant, a polyethylene glycol, a sorbitan fatty acid ester ethoxylate, or a combination thereof). [0030] The combinations (e.g., fungicidal compositions) include a pigment (e.g., a polychlorinated (Cu II) phthalocyanine). 40 Definitions

[0031] As used herein, the term "oil-in-water emulsion" refers to a mixture in which one of the paraffinic oil and water (e.g., the paraffinic oil) is dispersed as droplets in the other (e.g., the water). In some implementations, an oil-in-water 45 emulsion is prepared by a process that includes combining the paraffinic oil, water, and any other components and the paraffinic oil and applying shear until the emulsion is obtained (typically a white milky color is indicative of the formation of an emulsion in the absence of any pigment; a green color is observed in the presence of a pigment). In other implementations, an oil-in-water emulsion is prepared by a process that includes combining the paraffinic oil, water, and any other components in the mixing tank and sprayed through the nozzle of a spray gun. 50 [0032] As used herein, the term "control a fungal pathogen of a plant" or "control a disease caused by a fungal pathogen" (and the like) means to diminish, ameliorate, or stabilize the disaease and/or any other existing unwanted condition or side effect that is caused by the association of a fungal pathogen with the plant. [0033] In certain implementations, the combinations, e.g., fungicidal compositions, exhibit a synergistic response, for example in controlling a fungal pathogen in a crop plant. In certain implementations, the combinations, e.g., fungicidal 55 compositions, may be synergistic fungicidal compositions for treating a fungal pathogen in crop plants. In selected implementations, the fungicidal compositions may exhibit a synergistic response, for example in controlling stem rusts in crop plants. As for example is suggested by Burpee and Latin (Plant Disease Vol. 92 No. 4, April 2008, 601-606), the term "synergy", "synergistic", or the like, may refer to the interaction of two or more agents so that their combined effect

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is greater than the sum of their individual effects, this may include, in the context of the invention, the action of two or more fungicidal agents in which the total response of a fungus to the fungicidal agent combination is greater than the sum of the individual components. Applying the approach to identifying synergy a set out in S.R. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967), expected efficacy, E, may 5 be expressed as: E=X+Y(100-X)/100, where X is the efficacy, expressed in % of the untreated control, of a first composition, and Y is the efficacy, expressed in % of the untreated control, of the second composition. [0034] The details of one or more implementations of the combinations and methods described herein are set forth in the accompanying description below. Other features and advantages of the combinations and methods described herein will be apparent from the description and drawings, and from the claims. 10 DESCRIPTION OF DRAWINGS

[0035]

15 Figure 1 is an image of a leaf blade of a wheat plant displaying splotch blot disease after inoculation with Bipolaris sorokiniana without prior treatment with a fungicidal composition. Figure 2 is an image of a leaf blade of a wheat plant inoculated with Bipolaris sorokiniana following foliar application of a fungicidal composition comprising Civitas™. Harmonizer™, and Folicur™ seven days before inoculation. Figure 3 is an image of a leaf blade of a wheat plant inoculated with Bipolaris sorokiniana following soil drench 20 application of a fungicidal composition comprising Civitas™ and Harmonizer™ seven days before inoculation. Figure 4 is an image of a leaf blade of a wheat plant displaying splotch blot disease after inoculation with Puccinia triticina without prior treatment with a fungicidal composition. Figure 5 is an image of a leaf blade of a wheat plant inoculated with Puccinia triticina following foliar application of a fungicidal composition comprising Civitas™. Harmonizer™, and Folicur™ seven days before inoculation. 25 Figure 6 is an image of a leaf blade of a wheat plant inoculated with Puccinia triticina following soil drench application of a fungicidal composition comprising Civitas™ and Harmonizer™ seven days before inoculation.

DETAILED DESCRIPTION

30 [0036] The present invention relates to the use of a fungicidal composition comprising: a paraffinic oil, an emulsifier, a copper phthalocyanine pigment and a silicone surfactant and wherein:the ratio of the paraffinic oil to the pigment is from about 5:1 to 100:1; the weight ratio of the paraffinic oil to the emulsifier is from 10:1 to 500:1; and the weight ratio of the pigment to the silicone surfactant is from 2:1 to 50:1, for controlling infection of a crop plant by a fungal pathogens. Also disclosed are combinations containing a paraffinic oil and one or more emulsifiers, one or more pigments, one or 35 more silicone surfactants, optionally one or more anti-settling agents, optionally one or more conventional chemical fungicides (e.g., a DMI or a QoI), and water. In some implementations, the combinations can be in the form of a single composition (e.g., which is contained within a storage pack or a vessel (e.g., a tank) suitable for applying the composition to a plant,e.g., crop plant).Typically, the composition isapplied to a plant after dilution with water.In other implementat ions, the combinations can include two or more separately contained (e.g., packaged) compositions, each containing one or 40 more of the above-mentioned components. Said compositions can be combined and applied to a plant typically after dilution with water; or each composition can be applied separately to the same plant either simultaneously or sequentially, and typically after dilution with water. This disclosure also features methods of using the combinations for controlling infection of a vascular crop plant by a fungal pathogen as well as methods of formulating combinations that include both oil and water as oil-in-water (O/W) emulsions. 45 I. Components

[A] Conventional Chemical Fungicides

50 [0037] The combinations include isomers such as geometrical isomers, optical isomers based on asymmetric carbon, stereoisomers and tautomers of the compounds described herein and are not limited by the description of the compounds for the sake of convenience.

[1] 55 [0038] In some implementations, the conventional fungicide is a DMI fungicide. [0039] In certain implementations, the DMI fungicide is at least one fungicide selected from the group consisting of tetraconazole, tebuconazole, propioconazole, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole,

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diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, prothioconazole, simeconazole, triadimefon, triadimenol, triticonazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenarimol, nuarimol, triforine, and pyrifenox. 5 [0040] In certain implementations, the DMI fungicide is at least one fungicide selected from the group consisting of tetraconazole, tebuconazole, and propioconazole. Tetraconazole can be obtained commercially, for example, as a product identified as Domark™ (available from Valent). Tebuconazole can be obtained commercially, for example, as a product identified as Folicur™ (available from Bayer Crop Science). Propioconazole can be obtained commercially, for example, in the product identified as Quilt™ (available from Syngenta). 10 [0041] In other implementations, the DMI fungicides described herein can be synthesized using conventional techniques known in the art of synthetic organic chemistry.

[2]

15 [0042] In some implementations, the conventional fungicide is a QoI fungicide. [0043] In certain implementations, the QoI fungicide is at least one fungicide selected from the group consisting of pyraclostrobin, azoxystrobin, fluoxastrobin, trifloxystrobin, coumoxystrobin, dimoxystrobin, enoxastrobin, famoxadone, fenamidone, fenaminostrobin, flufenoxystrobin, kresoxim-methyl, metominostrobin, orysastrobin, pyraoxystrobin picoxystrobin, pyrametastrobin, pyribencarb, and triclopyricarb. 20 [0044] In certain implementations, the QoI fungicide is at least one fungicide selected from the group consisting of pyraclostrobin, azoxystrobin, fluoxastrobin, and trifloxystrobin. [0045] In certain implementations, the QoI fungicide is at least one fungicide selected from the group consisting of pyraclostrobin and azoxystrobin. [0046] In certain implementations, the QoI fungicide is methylE )-2-{2-[(3-butyl-4-methyl-2-oxo-2 (2 H-chromen-7- 25 yl)oxymethyl]phenyl}-3-methoxyacrylate (coumoxystrobin): CAS No. 850881-70-8. [0047] In certain implementations, the QoI fungicide E)-2-(methoxyimino)- is ( N-methyl-2-[a-(2,5-xylyloxy)-o- tolyl]acetamide (dimoxystrobin): CAS No. 149961-52-4. [0048] In certain implementations, the QoI fungicide is enoxastrobin. In alternative implementations, the QoI fungicide may be, for example, (RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione (famoxadone): CAS No. 30 131807-57-3. [0049] In certain implementations, the QoI fungicide is (S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one (fenamidone): CAS No. 161326-34-7. [0050] In certain implementations, the QoI fungicide is fenaminostrobin. [0051] In certain implementations, the QoI fungicide is flufenoxystrobin. 35 [0052] In certain implementations, the QoI fungicide is methyl ( E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate (kresoxim-methyl): CAS No. 143390-89-0. [0053] In certain implementations, the QoI fungicide is ( E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (metominostrobin): CAS No. 133408-50-1. [0054] In certain implementations, the QoI fungicide may be, for example, (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)- 40 5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl)-N-methylacetamide (orysastrobin): CAS No. 248593-16-0. [0055] In certain implementations, the QoI fungicide is methylE )-2-(2-{[3-(4-chlorophenyl)-l-methylpyrazol-5- (2 yl]oxymethyl}phenyl)-3-methoxyacrylate (pyraoxystrobin): CAS No. 862588-11-2. [0056] Incertain implementations, theQoI fungicideis methyl (2 E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxyme- 45 thyl]phenyl}acrylate (picoxystrobin): CAS No. 117428-22-5. [0057] In certain implementations, the QoI fungicide is pyrametastrobin. [0058] In certain implementations, the QoI fungicide is methyl {2-chloro-5-[(1E)-1-(6-methyl-2-pyridylmethoxyimi- no)ethyl]benzyl}carbamate (pyribencarb): CAS No. 799247-52-2. [0059] In certain implementations, the QoI fungicide is triclopyricarb. 50 [0060] In certain implementations, the QoI fungicide is carbamic acid, [2-[[[1-(4-chlorophenyl)-1 H-pyrazol-3-yl]oxy]methyl]-phenyl]methoxy-,methyl ester (pyraclostrobin). Pyraclostrobin may be commercially available, for example, as a product identified as Insignia™ (available from BASF Corporation, 26 Davis Drive, Research Triangle Park, NC 27709). [0061] In certain implementations, the QoI fungicide is methyl (E)-2-{2-[6-(2-cyano-phenoxy)pyrimidin-4-yloxy]phenyl}- 3-methoxy-acrylate (azoxystrobin). Azoxystrobin may be commercially available, for example, as a product identified as 55 Heritage™ (available from Syngenta Crop Protection, Inc., Greensboro, NC 27409). [0062] In certain implementations, the QoI fungicide is [(1E)-[2-[[6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy]phenyl]5,6-dihydro-1,4,2-dioxazin-3-yl]methanone-O-methyloxime] (fluoxastrobin). Fluoxastrobin may be commercially available, for example, as a product identified as Disarm™ (available from Arysta LifeScience North America, LLC,

7 EP 2 713 749 B1

15401 Weston Parkway, Suite 150, Cary, NC 27513). [0063] In certain implementations, the QoI fungicide is benzeneacetic acid, (E,E)-alpha-(methoxyimino)-2((((1-(3-trifluoromethyl)phenyl)ethylidene)-amino)oxy)methyl)-,methyl ester (trifloxystrobin). Trifloxystrobin may be commercially available, for example, as a product identified as Compass™ (available from Bayer Environmental Science, 2T. W. 5 Alexander Drive, Research Triangle Park, NC 27709). [0064] In otherimplementations, the QoIfungicides described herein can be synthesizedusing conventional techniques known in the art of synthetic organic chemistry.

[B] Paraffinic oil 10 [0065] The paraffinic oil confers properties (e.g., fungicidal properties) that are useful for promoting the health of a plant (e.g., crop plant). While not wishing to be bound by theory, it is believed that the paraffinic oil is able to provoke an induced systemic resistance (ISR) response, a systemic acquired resistance (SAR), or other defense response in a plant. 15 [1]

[0066] In some implementations, the paraffinic oil includes an oil enriched in paraffin. [0067] In certain implementations, the paraffinic oil includes a paraffin having from 12 carbon atoms to 50 carbon 20 atoms (e.g., 12 carbon atoms to 40 carbon atoms, 16 carbon atoms to 35 carbon atoms, 12 carbon atoms to 21 carbon atoms; e.g., 16 carbon atoms to 35 carbon atoms). [0068] In certain implementations, the paraffinic oil includes a paraffin having an average number of carbon atoms that is less than or equal to about 20 (e.g., 16). [0069] In certain implementations, the paraffinic oil includes a paraffin having an average number of carbon atoms of 25 from 16 to 30 e.g., 23 or 27). [0070] In certain implementations, the paraffinic oil includes a paraffin having from 16 carbon atoms to 35 carbon atoms and an average number of carbon atoms of 23. [0071] In certain implementations, the paraffin is an isoparaffin (e.g., a synthetic isoparaffin manufactured from two- stage Severe Hydrocracking/Hydroisomerization process). 30 [0072] In some implementations, a paraffin is present in the paraffinic oil in an amount, that is at least 80% (e.g., at least 90%, at least 99%).

[2]

35 [0073] In some implementations, the paraffinic oil has been refined to remove compounds that are associated with plant injury, for example, aromatic compounds or compounds containing sulfur, nitrogen, or oxygen. In certain implementations, the paraffinic oil includes relatively low levels of aromatic compounds and/or compounds containing sulfur, nitrogen, or oxygen, e.g., less than 10 weight percent (less than 5 weight percent, less than 2 weight percent, less than 0.5 weight percent) of aromatic compounds and/or compounds containing sulfur, nitrogen, or oxygen. 40 [3]

[0074] Non-limiting examples of suitable paraffinic oils include, HT60, HT100, High Flash Jet, LSRD, and N65DW (available from Petro-Canada, Calgary, AB, Canada). 45 [C] Emulsifier

[0075] The combinations include both paraffinic oil, emulsifier, and water. It can be advantageous to store and/or apply such combinations as oil-in-water (O/W) emulsions. 50 [0076] Emulsions tend to be thermodynamically unstable due to excess free energy associated with the surface of the dispersed droplets such that the particles tend to flocculate (clumping together of dispersed droplets or particles) and subsequently coalesce (fusing together of agglomerates into a larger drop or droplets) to decrease the surface energy. If these droplets fuse, the emulsion will "break" (i.e., the phases will separate) destroying the emulsion, which in some cases can be detrimental to the storage shelf-life of the combinations. While not wishing to be bound by theory, 55 it is believed that the addition of one (or more) emulsifying agents or emulsifiers can prevent or slow the "breaking" of an emulsion. As the skilled artisan will appreciate, the type and concentration of a particular emulsifying agent will depend, inter alia, on the emulsion phase components and the desired result.

8 EP 2 713 749 B1

[1]

[0077] In some implementations, the emulsifier is a "fast break" or "quick break" emulsifier. While not wishing to be bound by theory, it is believed that a "fast break" or "quick break" emulsifier allows the paraffinic oil to be quickly release d 5 from the O/W emulsion upon application to the turfgrass for contact, e.g., with a fungal pathogen. When a "fast break" or "quick break" emulsifier is present in a suitable amount (for example a selected proportion or ratio with respect to the paraffinic oil), the resulting "fast break" or "quick break" O/W emulsion quickly releases the oil phase upon application to the turfgrass. As such, there is less runoff of the O/W emulsion from the grass blades (as compared to more stable O/W emulsions) resulting in more oil adhering to the turfgrass for a longer period of time to more effectively contact and 10 control, e.g., associated fungal pathogen. In certain implementations, the oil phase resides on the turfgrass for a period of not less than one hour. In certain implementations, the oil phase resides on the turfgrass for a period of from not less than 1 hour but not more than 30 days. In certain implementations,, the "fast break" or "quick break" emulsion may be, for example, an emulsion having an oil phase that, after mixing with water, is reconstituted in 0.5 to 15 minutes according to the following test: 15 1. Fill 100mL graduated cylinder with tap water.

2. Add 1mL of emulsified oil.

20 3. Invert graduated cylinder 5 times.

4. Using a stop watch and human observation, measure how long it takes for the oil phase to reconstitute after inversion (step 3).

25 [0078] In some implementations, the oil phase is reconstituted in from 2 minutes to 5 minutes according to the test described above. In some instances, the "fast break" or "quick break" property of the O/W emulsion is balanced with the need to provide an O/W emulsion with a suitable shelf life under suitable storing conditions, and for a suitable timeframe.

30 [2]

[0079] In some implementations, the emulsifier is (or includes) one (or more of the following) a natural or synthetic alcohol ethoxylate, an alcohol alkoxylate, an alkyl polysaccharide, a glycerol oleate, a polyoxyethylene-polyoxypropylene block copolymer, an alkyl phenol ethoxylate, a polymeric surfactant, a polyethylene glycol, a sorbitan fatty acid ester 35 ethoxylate, or any combination thereof. [0080] In certain implementations, the emulsifier is (or includes) a natural or synthetic alcohol ethoxylate, a polymeric surfactant, a sorbitan fatty acid ester, or any combination thereof. [0081] In certain implementations, the natural or synthetic alcohol ethoxylate is a polyoxyethylene (4 to 12) lauryl ether (C12), polyoxyethylene (10) cetyl ether (C16), polyoxyethylene (10) stearyl ether (C18), polyoxyethylene (10) oleyl ether 40 (C18 mono-unsaturated), a polyoxyethylene (2 to 11) C12-C15 alcohol, a polyoxyethylene (3 to 9) C11-C14 alcohol, a polyoxyethylene (9) C12-C14 alcohol, a polyoxyethylene (11) C16-C18 alcohol, a polyoxyethylene (20) C12-C15 alcohol, or any combination thereof. For example, the natural or synthetic alcohol ethoxylate can be a polyoxyethylene (4 to 7) lauryl ether (C12), polyoxyethylene (10) cetyl ether (C16), a polyoxyethylene (2 to 11) C12-C15 alcohol, a polyoxyethylene (3 to 9) C11-C14 alcohol, a polyoxyethylene (9) C12-C14 alcohol, or any combination thereof. As another example, the 45 alcohol alkoxylate can be a butyl ether polyoxyethylene/polyoxypropylene block copolymer. [0082] In certain implementations, the emulsifier is (or includes) an alkyl polysaccharide, e.g., a C8-C11 alkylpolysac- charide or any combination thereof. [0083] In certain implementations, the emulsifier is (or includes) a glycerol oleate, e.g., a glycerol mono-, di-, tri-oleate, or any combination thereof. 50 [0084] In certain implementations, the emulsifier is (or includes) a polyoxyethylene-polyoxypropylene block copolymer, e.g., a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight (or relative molar mass) of from 1100 to about 11400 and 10 to 80% (ethylene oxide) EO. [0085] In certain implementations, the emulsifier is (or includes) an alkyl phenol ethoxylate, e.g., a nonyl phenol ethoxylate, a dodecyl phenol ethoxylate, or any combination thereof. For example, the nonyl phenol ethoxylate can be 55 a polyoxyethylene (2 to 8) nonylphenol. [0086] In certain implementations, the emulsifier is (or includes) a polymeric surfactant, e.g., a graft copolymer, a random copolymer, or any combination thereof. For example, the graft copolymer can be a polymethacrylic acid and acrylate with polyoxyethylene chains. For example, the random copolymer can be a random copolymer having ester

9 EP 2 713 749 B1

and ether groups. [0087] In certain implementations, the emulsifier is (or includes) a polyethylene glycol, e.g., a polyethylene glycol having a molecular weight ("MW") (or relative molar mass) of from 200 to 8000, e.g., MW 400 PEG dioleate; or MW600 PEG dioleate. 5 [0088] In certain implementations, the emulsifier is (or includes) a sorbitan fatty acid ester ethoxylate, e.g., polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, or any combination thereof. For example, the sorbitan fatty acid ester can be a sorbitan tristearate, a sorbitan triolate, or any combination thereof. [0089] In certain implementations, the emulsifier is (or includes) an alkyl phenol ethoxylate, a mixture of an ethoxylated 10 alcohol and a glycerol oleate, or any combination thereof. [0090] In certain implementations, the emulsifier is (or includes) a mixture of an ethoxylated alcohol and a glycerol oleate, e.g.: a C10 to C16 alcohol ethoxylate and a glycerol oleate combination; or polyoxyethylene lauryl ether, C10 to C16 alcohol ethoxylates, and glycerol oleate; or ethoxylated alcohols having primary C5-C20 carbon chains with an average of about 2 to about 7 ethoxylation groups, and a glycerol oleate; or a polyoxyethylene (11) C16-18 alcohol. 15 [0091] In certain implementations, the emulsifier is (or includes) a sorbitan tristearate. [0092] Non-limiting examples of suitable emulsifiers include AL3149 (available from Uniqema), AL3313 (available from Uniqema), PC Emuls Green (available from Petro-Canada, Calgary, AB, Canada), Lutensol™ AT11 (available from BASF), SPAN65 (available from Uniqema), and S-MAZ™65K (available from BASF).

20 [3]

[0093] In some implementations, the weight ratio of the paraffmic oil to the emulsifier is from 95:5 to 99.95:0.05 (e.g., from 98:2 to 99.9:0.1, from 98:2 to 99.5:0.5). By way of example, the weight ratio of the paraffinic oil to the emulsifier can be 98.8:1.2; 99.2:0.8; 99.4:0.6; 99.5:0.5; 99.94:0.06; 99.95:0.05; or 99.25:0.75. 25 [D] Pigment

[0094] The combinations include one (or more) pigments. The pigments provide color to the plant being treated and/or in some implementations, the pigment(s) and the paraffinic oil can exhibit a greater than additive effect in promoting the 30 health of a plant (e.g., controlling a fungal pathogen of a plant; see, for example, WO 2009/155693). [0095] The pigment is a copper phthalocyanine. [0096] In certain implementations, the copper phthalocyanine is a non-halogenated copper phthalocyanine, e.g., a nonchlorinated copper phthalocyanine. As an example, the pigment can be Phthalocyanine Blue BN (CAS 147-14-8). [0097] In certain implementations, the copper phthalocyanine is a halogenated copper phthalocyanine. As an example, 35 thepigment can be PhthalocyanineGreen 6G(CAS 14302-13-7). As anotherexample, the pigmentcan be polychlorinated (Cu II) phthalocyanine, such as Phthalocyanine Green G (CAS 1328-45-6 and 1328-53-6). [0098] Non-limiting examples of suitable pigments include Sunsperse™ Green 7 (available from Sun Chemical Corp. Performance Pigments Cincinnati, OH, USA), Sunsperse™ EXP 006-102 (available from Sun Chemical Corp. Perform- ance Pigments, Cincinnati, OH, USA), and Pigment Green 7 powder (available from Hercules Exports, Mumbai, India). 40 [E] Silicone Surfactant

[0099] The combinations include one (or more) silicone surfactants.

45 [1]

[0100] In some implementations, the silicone surfactant is (or includes) a silicone polyether. [0101] In certain implementations, the silicone surfactant is (or includes) a silicone polyether having a suitable alkoxy group with hydrogen end groups (H-capped), methyl end groups (CH 3-capped), or acetyl end groups (COCH 3-capped). 50 In certain implementations, the silicone surfactant is (or includes) a trisiloxane having a suitable alkoxy group with hydrogen end groups (H-capped), methyl end groups (CH 3-capped), or acetyl end groups (COCH3-capped). [0102] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I:

10 EP 2 713 749 B1

10 in which R is H, CH3 or COCH3; x is 1 to 24; and n is 0 or ≥ 1. [0103] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein R = H; x = 1 to 24; and n = 0; e.g., a silicone polyether of the formula I wherein n = 0; x = 1 - 24; the average x = 8 - 10; and R = H. [0104] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein 15 R = H; x = 1 to 24; and n ≥ 1. [0105] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein R = CH3; x = 1 to 24; and n = 0. [0106] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein R = CH3; x = 1 to 24; and n ≥ 1. 20 [0107] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein

R = COCH3; x = 1 to 24; and n = 0; e.g., a silic one polyether of the formula I wherein n = 0; x = 1 - 24, the average x = 8 - 10; and R = COCH 3. [0108] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula I wherein R = COCH3; x = 1 to 24; and n ≥ 1. 25 [0109] In certain implementations, the silicone surfactant is (or includes) an H-capped dimethyl methyl (polyethylene oxide) silicone polymer; e.g., having a molecular weight (or relative molar mass) from 200 to 6000. [0110] In certain implementations, the silicone surfactant is (or includes) a silicone polyether of the formula II:

35 wherein c = 2 - 16; and b = 2 - 70. In certain implementations, the average b = 44. In certain implementations, the average c = 10. In certain implementations, the average b = 44, and the average c = 10. [0111] In certain implementations, the silicone surfactant is (or includes) an H-capped trisiloxane, such as a silicone polyether of the formula III: 40

wherein d = 1- 24. In certain implementations, d = 1 - 20. In certain implementations, the average d = 8 - 10 (e.g., 8). [0112] In certain implementations, the silicone surfactant is (or includes) a silicone copolyol, containing a hydrogen 50 end group and one pendant polyethylene oxide group and has an average molecular weight between about 600 to about 1000 Daltons. In certain implementations, the silicone surfactant is (or includes) a trisiloxane with an ethoxylated alkyl group having a hydrogen end group (H-End); e.g., having a number of ethoxylation groups in the range of 1 - 20. In certain implementations, the silicone surfactant the silicone surfactant is (or includes) a methyl (propylhydroxide, ethoxylated) bis (trimethylsiloxy) silane; e.g., a dimethyl, methyl (polyethylene oxide) silicone polymer. 55 [2]

[0113] In some implementations, commercial preparations of the silicone surfactants may or may not contain small

11 EP 2 713 749 B1

amounts of polyethylene glycols (PEG) or other low molecular weight polydimethyl siloxanes (PDMS). [0114] In some implementations, the silicone surfactant further includes a polyethylene glycol. [0115] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV:

5 1 2 R -O-(CH2CH2O)f-R

1 2 wherein R = H or CH2=CH-CH2 or COCH3; R = H or CH2=CH-CH2 or COCH3; and f ≥ 1. [0116] In certain implementations, the polyethylene glycol has a relatively low molecular weight, e.g. from 300 Daltons to 1500 Daltons. In certain implementations, the polyethylene glycol is a low molecular weight polyethylene glycol allyl 10 ether, such as a low molecular weight polyethylene glycol mono-allyl ether having an average molecular of from about 300 to about 600 Daltons and having from 1 to 20 moles of ethylene glycol with an average ethylene oxide unit (EO) of 8 to 10. [0117] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV 1 2 wherein R = CH2=CH-CH2, R = H, and f = 1-20 with an average f = 8, a polyethylene glycol of the formula IV wherein 15 1 2 1 R = CH2=CH-CH2 or COCH3, and R = COCH3, a polyethylene glycol of the formula IV wherein R = CH2=CH-CH2, and R2 = H, or any combination thereof. [0118] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV 1 2 1 wherein R = CH 2=CH-CH2 or COCH 3, and R = COCH3, a polyethylene glycol of the formula IV wherein R = CH 2=CH- 2 CH2, and R = H, or any combination thereof. 20 [0119] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV 1 2 wherein R = CH2=CH-CH2, R = H, and f = 1-20 with an average f = 8. [0120] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV 1 2 wherein R = CH2=CH-CH2 or COCH3, and R = COCH3. [0121] In certain implementations, the polyethylene glycol is (or includes) a polyethylene glycol of the formula IV 25 1 2 wherein R = CH2=CH-CH2, and R = H. [0122] Non-limiting examples of suitable polyethylene glycols may include Polyglykol A500 (available from Clariant). [0123] In certain implementations, the silicone surfactant includes from 10 to 30 weight percent of a polyethylene glycol as described anywhere herein.

30 [3]

[0124] Non-limiting examples of suitable silicone surfactants may include Sylgard™ 309 (available from Dow Corning, Midland, MI, USA), Silfsurf™ A008-UP (available from Siltech Corp. Toronto, ON, Canada), Lambent MFF 199 SW (available from Lambent Technologies Corp., Gurnee, IL, USA), and Lambent MFF 159-100 (available from Lambent 35 Technologies Corp., Gurnee, IL, USA).

[F] Anti-Settling Agent

[0125] In some implementations, the combination can include one (or more) "anti-settling agents," which reduce the 40 likelihood of having solids suspended in a dispersion from settling out under the influence of gravity. [0126] In some implementations, the anti-setting agent is (or includes) a metal oxide and/or an organically modified clay. [0127] In some implementations, the anti-setting agent is (or includes) a metal oxide. [0128] In certain implementations, the anti-setting agent is (or includes) a fumed metal oxide and/or a precipitated metal oxide. 45 [0129] In certain implementations, the anti-setting agent is (or includes) one or more of the following forms of silica: precipitated silica (e.g., an untreated, precipitated silica) or fumed silica (e.g., an untreated, fumed silica). As used herei n, the term "untreated fumed silica", or the like, is used to refer to a hydrophilic fumed silica. As used herein, the term "treated fumed silica", or the like, is used to refer to a hydrophobic fumed silica. [0130] In some implementations, the anti-settling agent is (or includes) an organically modified clay. In certain imple- 50 mentations, the anti-setting agent is (or includes) one or more of the following organically modified clays: an organically modified smectite clay, an organically modified hectorite clay, an organically modified bentonite clay, an organically modified montmorillonite clay and an organically modified attapulgite clay. [0131] In certain implementations, the organically modified clay is activated by a chemical activator. [0132] In certain implementations, the chemical activator includes a low-molecular-weight polar organic compound, 55 e.g., a least one compound selected from the group consisting of a low-molecular weight ketone, a low-molecular weight alcohol and propylene carbonate. [0133] In certain implementations, the chemical activator includes water and at least one compound selected from the group consisting of a low-molecular weight ketone, a low-molecular weight alcohol and propylene carbonate.

12 EP 2 713 749 B1

[0134] In certain implementations, the chemical activator includes a low-molecular weight ketone; or a low-molecular weight ketone and water (such as a low molecular weight ketone and water in a weight ratio of 95/5). An example of a low-molecular weight ketone is acetone. [0135] In certain implementations, the chemical activator includes a low-molecular weight alcohol; or a low-molecular 5 weight alcohol and water (such as a low-molecular weight alcohol and water in a weight ratio of 95/5). Examples of low- molecular weight alcohols include methanol or ethanol. [0136] In certain implementations, the chemical activator includes propylene carbonate; or propylene carbonate and water (such as, propylene carbonate and water in a weight ratio of 95/5).

10 [G] Water

[0137] In some implementations, the combinations can further include water, e.g., as a diluent, e.g., as a diluent added prior to application of the combinations to a plant (e.g., a turfgrass), such as distilled water or other waters having a low mineral electrolyte content. 15 [H] Other Components

[0138] In some implementations, the combinations further include one or more other components that are customary additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or components 20 that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) and/or one or more other active components. As an example, the combinations can further include customary additives or adjuvants that may be present in a commercially available conventional chemical fungicide. [0139] In some implementations, the combinations include only combinations of the components set forth is sections [A] through [G] above. 25 [0140] In certain implementations, the combinations do not include one or more other components that are customary additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or components that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) and/or one or more other active components that are other than conventional chemical fungicides. [0141] In certain implementations, the combinations are free of one or more other components that are customary 30 additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or components that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) and/or one or more other active components that are other than conventional chemical fungicides; (e.g., the combinations contain less than 5%, less than 4%, less than 3%, less than 2%, less than 1% (w/w or w/v) of one or more other components that are customary additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or 35 components that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) and/or one or more other active components that are other than conventional chemical fungicides. [0142] In some implementations, the combinations are substantially free of one or more other components that are customary additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or components that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) 40 and/or one or more other active components that are other than conventional chemical fungicides (e.g., the combinations contain less than 0.5%, less than 0.2, less than 0.1, less than 0.05% (w/w or w/v), do not include a detectable amount of one or more other components that are customary additives or adjuvants for the preparation of compositions in the field of turf or field crop protection and/or components that are inert (e.g., may not materially affect the activity and/or overall performance of the combinations) and/or one or more other that are other than conventional chemical fungicides. 45 II. Application of Combinations

[0143] In general, the combinations can be applied to the plant by conventional methods known in the art, e.g., spraying, misting, sprinkling, pouring, or any other suitable method. The compositions may be reapplied as required. 50 [0144] The combinations include both paraffinic oil and water as oil-in-water (O/W) emulsions. In some implementations, an oil-in-water emulsion is prepared by a process that includes combining the paraffinic oil, water, and any other components and the paraffinic oil and applying shear until the emulsion is obtained. In other implementations, an oil-in- water emulsion is prepared by a process that includes combining the paraffinic oil, water, and any other components at the nozzle of a spray gun. 55 [0145] In other implementations, the combinations can include two or more separately contained (e.g., packaged) compositions, each containing one or more of the above-mentioned components. Said compositions can be combined and applied to a plant (e.g., crop plant) with or without prior dilution with water; or each composition can be applied separately to the same plant (e.g., crop plant) either simultaneously or sequentially, and each independently applied

13 EP 2 713 749 B1

with or without prior dilution with water. [0146] In the above-described implementations, application of any one (or more) compositions can be repeated one or more times. [0147] In some implementations, any one or more of the following can apply: 5 • the paraffinic oil is applied to a plant (e.g., turf grass) at a rate from 3.22 to 103 L/Ha (1.0 oz/1000 square ft to 32 oz/1000 square ft) (e.g., from 25.76 to 51.52L/Ha (8.0 oz/1000 square ft to 16 oz/1000 square ft)); • the paraffinic oil is used or applied to the plant (e.g., turf grass) at an interval rate of, for example, from 7 days to 90 days (e.g., from 7 days to 28 days, from 7 days to 21 days, from 7 days to 14 days, from 14 days to 21 days, 10 from 14 days to 28 days, 7 days, 10 days, 14, days, 21 days); • conventional chemical fungicide (e.g., one or more DMI fungicides and/or one or more QoI fungicides) is applied to a plant (e.g., crop plant) at a rate from 0.01 to 1.68 kg/Ha (0.01 lbs/acre to 1.50 lbs/acre); • DMI fungicide (e.g., propioconazole,) is applied to a plant (e.g., crop plant) at a rate from 0.017 to 0.67 kg/ha (0.015 lbs/acre to 0.6 lbs/acre) (e.g., from 0.07 to 0.28 kg/ha (0.060 lbs/acre to 0.25 lbs/acre)); or a rate from (e.g., tebu- 15 conazole, prothioconazole)0.02 to 0.5 kg/ha (0.02 to about 0.45 lbs./acre); or at a rate from (e.g., tetaconazole) 0.017 to 0.17 kg/ha (0.015 to about 0.15 lbs./acre); • QoI fungicide is applied to a plant (e.g., crop plant) at a rate from 0.01 to 0.56 kg/ha (0.01 lbs/acre to 0.50 lbs/acre) (e.g., azoxystrobin); or a rate from 0.02 to 0.45 kg/ha (0.02 lbs/acre to 0.40 lbs/acre) (e.g., pyraclostrobin); or a rate from and 20 • conventional chemical fungicide (e.g., one or more DMI fungicides and/or one or more QoI fungicides) is used or applied to the plant at an interval rate of from 14 to 84 days (e.g., from 21 to 84 days, or from 14 to 56 days, or from 21 to 56 days, or from 14 to 42 days, or from 21 to 42 days, or from 14 to 35 days, or from 21 to 35 days, or from 14 to 28 days, or from 21 to 28 days).

25 [0148] In certain implementations, the interval rates for the paraffinic oil and the conventional chemical fungicide (e.g., one or more DMI fungicides and/or one or more QoI fungicides) overlap (e.g., when tank-mixed and applied at the same time). In other implementations, the interval rates for the paraffinic oil and the conventional chemical fungicide (e.g., one or more DMI fungicides and/or one or more QoI fungicides) do not overlap (e.g., when applied separately and/or sequentially). 30 [0149] In some implementations, the combinations described herein can be prepared using the methods described in, for example, WO 2009/155693. [0150] The features described in section II above can be combined with any one or more of the features described in section I above. [0151] In some implementations, the fungal pathogen may be, for example, Gymnosporangium juniperi-virginianae, 35 Cronartium ribicola, Hemileia vastatrix Puccinia graminis, Puccinia coronata, Puccinia hemerocallidis, Puccinia persistens subsp. Triticina, Puccinia sriiformis, Puccinia triticina, Phakopsora meibomiae, Phakopsora pachyrhizi, Uromyces phaseoli, Uromyces appendeculatus, Fusarium graminearum, Bipolaris sorokiniana, or a combination thereof. In alternative implementations, the fungal disease may be, for example: cedar-apple rust, which attacks, for example, apple and pear and hawthorn); white pine blister rust, which attacks, for example, white pines and currants; coffee rust, which 40 attacks, for example, the coffee plant; wheat stem rust, which attacks, for example, Kentucky bluegrass, barley, and wheat; crown rust, which attacks, for example, oats and ryegrass; soybean rust, which attacks, for example, soybean and various legumes; leaf rust, which attacks, for example, wheat; bean rust which attacks, for example, bean; Daylily rust, which attacks, for example, Daylily; wheat rust in grains, also known as "brown" or "red rust’); "yellow" or "stripe rust", which attacks, for example, wheat; spot blotch, which attacks, for example, wheat; and Fusarium head blight, 45 which attacks, for example, wheat. [0152] In alternative implementations, the fungal pathogen may be, for example, a fungus that blights leaf tissue in a crop plant. In selected implementations, the crop plant pathogen is the fungal pathogenGymnosporangium juniperi- virginianae, and the disease may be, for example, cedar-apple rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Cronartium ribicola, and the disease may be, for example, white pine blister rust. In 50 selected implementations, the crop plant pathogen is the fungal pathogen, and the disease may be, for example, coffee rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Puccinia graminis, and the disease may be, for example, wheat stem rust. In selected implementations, the crop plant pathogen is the fungal pathogen Puccinia coronata, and the disease may be, for example, crown rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Phakopsora meibomiae or Phakospora pachyrhizi, and the disease may be, for example, 55 soybean rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Uromyces phaseoli, and the disease may be, for example, bean rust. In selected implementations, the crop plant pathogen is the fungal pathogen Puccinia hemerocallidis, and the disease may be, for example, Daylily rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Puccinia persistens subsp. triticina, and the disease may be, for example, brown

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rust or red rust. In selected implementations, the crop plant pathogen is the fungal pathogen Puccinia sriiformis, and the disease may be, for example, yellow rust or strip rust. In alternative implementations, the crop plant pathogen is the fungal pathogen Uromyces appendeculatus, and the disease may be, for example, bean rust. In selected implementations, the crop plant pathogen is the fungal pathogen Puccinia triticina, and the disease may be, for example, leaf rust. 5 In alternative implementations, the crop plant fungal pathogen is Fusarium graminearum and the disease may be, for example, Fusarium head blight. In selected implementations, the crop plant pathogen is the fungal pathogen Bipolaris sorokiniana, and the disease may be, for example, spot blotch. [0153] In various additional implementations wherein the crop plant is wheat, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 1, and the disease may be the corresponding disease of 10 wheat listed in the left column of Table 1.

Table 1. Fungal diseases of wheat. Disease Causative fungal pathogen(s)

15 Alternaria leaf blight Alternaria triticina Colletotrichum graminicola Anthracnose Glomerella graminicola [teleomorph] Ascochyta leaf spot Ascochyta tritici 20 Microdochium bolleyi Aureobasidium decay = Aureobasidium bolleyi Alternaria spp. Cladosporium spp. 25 Black head molds = sooty molds Epicoccum spp. Sporobolomyces spp. Stemphylium spp. and other genera Hymenula cerealis Cephalosporium stripe 30 = Cephalosporium gramineum Tilletia tritici = Tilletia caries Common bunt = stinking smut Tilletia laevis = Tilletia foetida 35 Cochliobolus sativus [teleomorph] Common root rot Bipolaris sorokiniana [anamorph] = Helminthosporium sativum Cottony snow mold Coprinus psychromorbidus 40 Fusarium spp. Fusarium pseudograminearum Gibberella zeae Crown rot = foot rot, seedling blight, dryland root rot Fusarium graminearum Group II [anamorph] 45 Gibberella avenacea Fusarium avenaceum [anamorph] Fusarium culmorum Dilophospora leaf spot = twist Dilophospora alopecuri 50 Downy mildew = crazy top Sclerophthora macrospora Dwarf bunt Tilletia controversa Claviceps purpurea Ergot Sphacelia segetum [anamorph] 55

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Disease Causative fungal pathogen(s) Tapesia yallundae 5 Ramulispora herpotrichoides [anamorph] = Pseudocercosporella herpotrichoides W-pathotype Eyespot = foot rot, strawbreaker Tapesia acuformis Ramulispora acuformis [anamorph] 10 = Pseudocercosporella herpotrichoides var. acuformis R- pathoytpe False eyespot Gibellina cerealis Flag smut Urocystis agropyri 15 Foot rot = dryland foot rot Fusarium spp. Pseudoseptoria donacis Halo spot = Selenophoma donacis Tilletia indica Kamal bunt = partial bunt 20 = Neovossia indica Puccinia triticina Leaf rust = brown rust = Puccinia recondita f.sp. tritici Puccinia tritici-duri 25 Phaeosphaeria herpotrichoides Leptosphaeria leaf spot = Leptosphaeria herpotrichoides Stagonospora sp. [anamorph] Ustilago tritici 30 = Ustilago segetum var. tritici Loose smut Ustilago segetum var. nuda Ustilago segetum var. avenae Phaeosphaeria microscopica Microscopica leaf spot 35 = Leptosphaeria microscopica Phoma spp. Phoma glomerata Phoma spot Phoma sorghina

40 = Phoma insidiosa Microdochium nivale Pink snow mold = Fusarium patch = Fusarium nivale Monographella nivalis [teleomorph] Clathrospora pentamera 45 Platyspora leaf spot = Platyspora pentamera Erysiphe graminis f.sp. tritici Blumeria graminis Powdery mildew = Erysiphe graminis 50 Oidium monilioides [anamorph] Pythium aphanidermatum Pythium arrhenomanes Pythium root rot Pythium graminicola 55 Pythium myriotylum Pythium volutum

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Disease Causative fungal pathogen(s) Rhizoctonia solani 5 Rhizoctonia root rot Thanatephorus cucumeris [teleomorph] Pyrenophora seminiperda Ring spot = Wirrega blotch = Drechslera campanulata Drechslera wirreganensis 10 Fusarium spp. Gibberella zeae Fusarium graminearum Group II [anamorph] Gibberella avenacea 15 Scab = head blight Fusarium avenaceum [anamorph] Fusarium culmorum Microdochium nivale = Fusarium nivale Monographella nivalis [teleomorph] 20 Myriosclerotinia borealis Sclerotinia snow mold = snow scald = Sclerotinia borealis Sclerotium rolfsii Sclerotium wilt (see Southern blight) Athelia rolfsii [teleomorph] 25 Septoria tritici Septoria blotch Mycosphaerella graminicola [teleomorph] Rhizoctonia cereal Sharp eyespot Ceratobasidium cereale [teleomorph] 30 Pythium spp. Pythium aristosporum Snow rot Pythium iwayamae Pythium okanoganense 35 Sclerotium rolfsii Southern blight = Sclerotium base rot Athelia rolfsii [teleomorph]

Typhula idahoensis 40 Speckledsnow mold = gray snowmold or Typhula Typhula incarnata blight Typhula ishikariensis Typhula ishikariensis var. canadensis Cochliobolus sativus [teleomorph] 45 Spot blotch Bipolaris sorokiniana [anamorph] = Helminthosporium sativum Phaeosphaeria avenaria f.sp. triticae Stagonospora avenae f.sp. triticae [anamorph] 50 = Septoria avenae f.sp. triticea Stagonospora blotch Phaeosphaeria nodorum Stagonospora nodorum [anamorph] = Septoria nodorum Puccinia graminis 55 Stem rust = black rust = Puccinia graminis f.sp. tritici (Ug99)

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Disease Causative fungal pathogen(s) Aspergillus spp. 5 Storage molds Penicillium spp. and others Puccinia striiformis Stripe rust = yellow rust Uredo glumarum [anamorph] 10 Gaeumannomyces graminis var. tritici Take-all Gaeumannomyces graminis var. avenae Pyrenophora tritici-repentis Tan spot = yellow leaf spot, red smudge Drechslera tritici-repentis [anamorph] 15 Phyllachora graminis Tar spot Linochora graminis [anamorph] Wheat Blast Magnaporthe grisea

20 Lagena radicicola Ligniera pilorum Zoosporic root rot Olpidium brassicae Rhizophydium graminis

25 [0154] In various additional embodiments wherein the crop plant is of the genus Zea, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 2, and the disease may be the corresponding disease of wheat listed in the left column of Table 2.

Table 2. Fungal diseases of maize. 30 Disease Causative fungal pathogen Colletotrichum graminicola Glomerella graminicola [teleomorph] Anthracnose leaf blight Anthracnose stalk rot Glomerella tucumanensis 35 Glomerella falcatum [anamorph] Aspergillus ear and kernel rot Aspergillus flavus Rhizoctonia solani = Rhizoctonia microsclerotia Banded leaf and sheath spot Thanatephorus cucumeris [teleomorph] 40 Black bundle disease Acremonium strictum = Cephalospirium acremonium Lasiodiplodia theobromae = Botryodiplodia Black kernel rot theobromae

45 Borde blanco Marasmiellus sp. Brown spot Black spot Physoderma maydis Stalk rot

50 Cephalosporium kernel rot Acremonium strictum = Cephalosporium acremonium Charcoal rot Macrophomina phaseolina Corticium ear rot Thanatephorus cucumeris = Corticium sasakii

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Disease Causative fungal pathogen Curvularia clavata 5 Curvularia eragrostidis = Curvularia maculans Cochliobolus eragrostidis [teleomorph] Curvularia inaequalis Curvularia intermedia 10 Cochliobolus intermedius [teleomorph] Curvularia leaf spot Curvularia lunata Cochliobolus lunatus [teleomorph] Curvularia pallescens Cochliobolus pallescens [teleomorph] 15 Curvularia senegalensis Curvularia tuberculata Cochliobolus tuberculatus [teleomorph] Didymella leaf spot Didymella exitalis 20 Diplodia frumenti Diplodia ear rot and stalk rot Botryosphaeria festucae [teleomorph] Diplodia ear rot Stalk rot Diplodia maydis 25 Seed rot Seedling blight Diplodia leaf spot or leaf streak Stenocarpella macrospora = Diplodia macrospora Brown stripe downy mildew Sclerophthora rayssiae 30 Crazy top downy mildew Sclerophthora macrospora = Sclerospora macrospora Green ear downy mildew Graminicola downy Sclerospora graminicola mildew Java downy mildew Peronosclerospora maydis = Sclerospora maydis 35 Peronosclerospora philippinensis = Sclerospora Philippine downy mildew philippinensis Sorghum downy mildew Peronosclerospora sorghi = Sclerospora sorghi Peronosclerospora spontanea = Sclerospora 40 Spontaneum downy mildew spontanea Sugarcane downy mildew Peronosclerospora sacchari = Sclerospora sacchari Dry ear rot Cob, kernel and stalk rot Niprospora oryzae Khuskia oryzae [teleomorph]

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Disease Causative fungal pathogen Alternaria alternata = Alternaria tenuis 5 Aspergillus glaucus Aspergillus niger Aspergillus spp. Botrytis cinerea 10 Botryotinia fuckeliana [teleomorph] Cunninghamella sp. Ear rots, minor Curvularia pallescens Doratomyces stemonitis = Cephalotrichum stemonitis Fusarium culmorum 15 Gonatobotrys simplex Pithomyces maydicus Rhizopus microsporus Rhizopus stolonifer = Rhizopus nigricans

20 Scopulariopsis brumptii Ergot Horse’s tooth Claviceps gigantea Sphacelia sp. [anamorph] Eyespot Aureobasidium zeae = Kabatiella zeae Fusarium ear and stalk rot Fusarium subglutinans = Fusarium moniliforme 25 Fusarium kernel, root and stalk rot, seed rot and Fusarium moniliforme seedling blight Gibberella fujikuroi [teleomorph] Fusarium avenaceum Fusarium stalk rot Seedling root rot Gibberella avenacea [teleomorph] 30 Gibberella zeae Gibberella ear and stalk rot Fusarium graminearum [anamorph] Botryosphaeria zeae = Physalospora zeae Gray ear rot Macrophoma zeae [anamorph] 35 Cercospora sorghi = Cercospora sorghi Gray leaf spot Cercospora leaf spot Cercospora zeae-maydis Exserohilum pedicellatum = Helminthosporium Helminthosporium root rot pedicellatum 40 Setosphaeria pedicellata [teleomorph] Cladosporium cladosporioides = Hormodendrum cladosporioides Hormodendrum ear rot Cladosporium rot Cladosporium herbarum 45 Mycosphaerella tassiana [teleomorph] Hyalothyridium leaf spot Hyalothyridium maydis Late wilt Cephalosporium maydis Alternaria alternata 50 Ascochyta maydis Ascochyta tritici Ascochyta zeicola Bipolaris victoriae = Helminthosporium victoriae 55 Cochliobolus victoriae [teleomorph] Cochliobolus sativus

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Disease Causative fungal pathogen Bipolaris sorokiniana [anamorph] = Helminthosporium 5 sorokinianum = H. sativum Epicoccum nigrum Leaf spots, minor Exserohilum prolatum = Drechslera prolata Setosphaeria prolata [teleomorph] 10 Graphium penicillioides Leptosphaeria maydis Leptothyrium zeae Ophiosphaerella herpotricha 15 Scolecosporiella sp. [anamorph] Paraphaeosphaeria michotii Phoma sp. Septoria zeae Septoria zeicola 20 Septoria zeina Northern corn leaf blight White blast Setosphaeria turcica Crown stalk rot Exserohilum turcicum [anamorph] = Helminthosporium Stripe turcicum 25 Northern corn leaf spot Cochliobolus carbonum Bipolaris zeicola [anamorph] = Helminthosporium Helminthosporium ear rot (race 1) carbonum Penicillium ear rot Penicillium spp. 30 Blue eye Penicillium chrysogenum Blue mold Penicillium expansum Penicillium oxalicum Phaeocytostroma ambiguum = Phaeocytosporella Phaeocytostroma stalk rot and root rot 35 zeae Phaeosphaeria leaf spot Phaeosphaeria maydis = Sphaerulina maydis Botryosphaeria festucae = Physalospora zeicola Physalospora ear rot Botryosphaeria ear rot Diplodia frumenti [anamorph] 40 Purple leaf sheath Hemiparasitic bacteria and fungi Pyrenochaeta stalk rot and root rot Phoma terrestris = Pyrenochaeta terrestris Pythium spp. Pythium root rot Pythium arrhenomanes 45 Pythium graminicola Pythium stalk rot Pythium aphanidermatum = Pythium butleri Red kernel disease Ear mold, leaf and seed rot Epicoccum nigrum Rhizoctonia zeae 50 Rhizoctonia ear rot Sclerotial rot Waitea circinata [teleomorph] Rhizoctonia solani Rhizoctonia root rot and stalk rot Rhizoctonia zeae

55 Alternaria alternata Cercospora sorghi Dictochaeta fertilis

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Disease Causative fungal pathogen Fusarium acuminatum Gibberella acuminata [teleomorph] 5 Fusarium equiseti Gibberella intricans [teleomorph] Fusarium oxysporum Fusarium pallidoroseum

10 Fusarium poae Root rots, minor Fusarium roseum Gibberella cyanogena Fusarium sulphureum [anamorph] Microdochium bolleyi 15 Mucor sp. Periconia circinata Phytophthora cactorum Phytophthora drechsleri Phytophthora nicotianae 20 Rhizopus arrhizus Rostratum leaf spot Helminthosporium leaf Setosphaeria rostrata = Helminthosporium rostratum disease, ear and stalk rot Rust, common corn Puccinia sorghi 25 Rust, southern corn Puccinia polysora Physopella pallescens Rust, tropical corn Physopella zeae = Angiopsora zeae

30 Sclerotium rolfsii Sclerotium ear rot Southern blight Athelia rolfsii [teleomorph] Bipolaris sorokiniana Bipolaris zeicola = Helminthosporium carbonum

35 Diplodia maydis Exserohilum pedicillatum Exserohilum turcicum = Helminthosporium turcicum Fusarium avenaceum Fusarium culmorum 40 Fusarium moniliforme Seed rot-seedling blight Gibberella zeae Fusarium graminearum [anamorph] Macrophomina phaseolina Penicillium spp. 45 Phomopsis spp. Pythium spp. Rhizoctonia solani Rhizoctonia zeae 50 Sclerotium rolfsii Spicaria spp. Selenophoma leaf spot Selenophoma sp. Sheath rot Gaeumannomyces graminis 55 Shuck rot Myrothecium gramineum

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Disease Causative fungal pathogen Monascus purpureus 5 Silage mold Monascus ruber Smut, common Ustilago zeae = Ustilago maydis Smut, false Ustilaginoidea virens

10 Smut, head Sphacelotheca reiliana = Sporisorium holci-sorghi Cochliobolus heterostrophus Southern corn leaf blight and stalk rot Bipolaris maydis [anamorph] = Helminthosporium maydis Southern leaf spot Stenocarpella macrospora = Diplodia macrospora 15 Cercospora sorghi Fusarium episphaeria Fusarium merismoides Fusarium oxysporum

20 Fusarium poae Fusarium roseum Stalk rots, minor Fusarium solani Nectria haematococca [teleomorph] Fusarium tricinctum 25 Mariannaea elegans Mucor spp. Rhopographus zeae Spicaria spp.

30 Aspergillus spp. Storage rots Penicillium spp. and other fungi Tar spot Phyllachora maydis Trichoderma viride = Trichoderma lignorum Trichoderma ear rot and root rot 35 Hypocrea sp. [teleomorph] White ear rot, root and stalk Stenocarpella maydis = Diplodia zeae Ascochyta ischaemi Yellow leaf blight Phyllosticta maydis 40 Mycosphaerella zeae-maydis [teleomorph] Zonate leaf spot Gloeocercospora sorghi

[0155] In various additional embodiments wherein the crop plant is barley, the fungal pathogen may be any one of the 45 fungal pathogens listed in the right hand column of Table 3, and the disease may be the corresponding disease of wheat listed in the left column of Table 3.

Table 3. Fungal diseases of barley. Disease Causative fungal pathogen(s) 50 Anthracnose[1] Colletotrichum cereale Manns Pyrenophora graminea Barley stripe = Drechslera graminea Hymenula cerealis 55 Cephalosporium stripe = Cephalosporium gramineum

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Disease Causative fungal pathogen(s) Cochliobolus sativus 5 = Bipolaris sorokiniana Common root rot, crown rot and seedling blight Fusarium culmorum Fusarium graminearum Gibberella zeae [teleomorph] 10 Downy mildew Sclerophthora rayssiae Dwarf bunt Tilletia controversa Claviceps purpurea Ergot Sphacelia segetum [anamorph] 15 Pseudocercosoporella herpotrichoides Eyespot Tapesia yallundae [teleomorph] Pseudoseptoria donacis Halo spot = Selenophoma donacis 20 Alternaria spp. Arthrinium arundinis[2] Kernel blight = black point Apiospora montagnei [teleomorph] Cochliobolus sativus 25 Fusarium spp. Ascochyta hordei Ascochyta graminea Ascochyta leaf spot[1][3] Ascochyta sorghi 30 Ascochyta tritici Drechslera teres Net blotch Pyrenophora teres [teleomorph] Net blotch (spot form) Drechslera teres f. maculata 35 Erysiphe graminis f.sp. hordei Powdery mildew = Blumeria graminis Oidium monilioides [anamorph] Pythium spp. 40 Pythium arrhenomanes Pythium root rot Pythium graminicola Pythium tardicrescens Rhizoctonia solani Rhizoctonia root rot 45 Thanatephorus cucumeris [teleomorph] Crown rust Puccinia coronata var. hordei Leaf rust Puccinia hordei Puccinia graminis f.sp. secalis Stem rust 50 Puccinia graminis f.sp. tritici Stripe rust = yellow rust Puccinia striiformis f. sp. hordei Fusarium spp. Scab = head blight Fusarium graminearum 55 Scald Rhynchosporium secalis

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Disease Causative fungal pathogen(s) Septoria passerinii 5 Septoria speckled leaf blotch Stagonospora avenae f.sp. triticae Rhizoctonia cerealis Sharp eyespot Ceratobasidium cereale [teleomorph] Covered smut Ustilago hordei 10 Ustilago nigra False loose smut = Ustilago avenae Ustilago nuda Loose smut = Ustilago tritici 15 Typhula incarnata Gray snow mold = Typhula blight Typhula ishikariensis Microdochium nivale

20 Pink snow mold = Fusarium patch = Fusarium nivale Monographella nivalis [teleomorph] Speckled snow mold Typhula idahoensis Pythium iwayamae

25 Snow rot Pythium okanoganense Pythium paddicum Myriosclerotinia borealis Snow scald = Sclerotinia snow mold = Sclerotinia borealis

30 Sclerotium rolfsii Southern blight Athelia rolfsii [teleomorph] Cochliobolus sativus Spot blotch Drechslera teres [anamorph]

35 Stagonospora avenae f.sp. triticae Phaeosphaeria avenaria f.sp. triticae [teleomorph] Stagonospora blotch Stagonospora nodorum = Septoria nodorum Phaeosphaeria nodorum [teleomorph] 40 Take-all Gaeumannomyces graminis var tritici Pyrenophora tritici-repentis = Pyrenophora trichostoma Tan spot Drechslera tritici-repentis [anamorph] 45 = Helminthosporium tritici-repentis Verticillium wilt[4][5] Verticillium dahliae Wirrega blotch Drechslera wirreganensis

50 [0156] In various additional embodiments wherein the crop plant is rice, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 4, and the disease may be the corresponding disease of wheat listed in the left column of Table 4.

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Table 4. Fungal diseases of rice. Disease Causative fungal pathogen(s) Ceratobasidium oryzae-sativae Aggregate sheath spot 5 Rhizoctonia oryzae-sativae [anamorph] Curvularia lunata Black kernel Cochliobolus lunatus [teleomorph] Pyricularia grisea 10 Blast (leaf, neck [rotten neck], nodal and collar) = Pyricularia oryzae Magnaporthe grisea [teleomorph] Cochliobolus miyabeanus Brown spot Bipolaris oryzae [anamorph] 15 Crown sheath rot Gaeumannomyces graminis Downy mildew Sclerophthora macrospora Eyespot Drechslera gigantea

20 False smut Ustilaginoidea virens Tilletia barclayana Kernel smut = Neovossia horrida Leaf smut Entyloma oryzae 25 Microdochium oryzae Leaf scald = Rhynchosporium oryzae Cercospora janseana Narrow brown leaf spot = Cercospora oryzae

30 Sphaerulina oryzina [teleomorph] Damage by many fungi including Pecky rice (kernel spotting) Cochliobolus miyabeanus Curvularia spp.

35 Fusarium spp. Microdochium oryzae Fusarium Microdochium Sarocladium Sarocladium oryzae and other fungi.

40 Fusarium spp. Pythium spp. Root rots Pythium dissotocum Pythium spinosum Cochliobolus miyabeanus 45 Curvularia spp. Fusarium spp. Seedling blight Rhizoctonia solani Sclerotium rolfsii 50 Athelia rolfsii [teleomorph] and other pathogenic fungi. Thanatephorus cucumeris Sheath blight Rhizoctonia solani [anamorph]

55 Sarocladium oryzae Sheath rot = Acrocylindrium oryzae Sheath spot Rhizoctonia oryzae

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(continued)

Disease Causative fungal pathogen(s) Stackbum (Alternaria leaf spot) Alternaria padwickii 5 Magnaporthe salvinii Stem rot Sclerolium oryzae [synanamorph] Achlya conspicua Achlya klebsiana 10 Fusarium spp. Water-mold (seed-rot and seedling disease) Pythium spp. Pythium dissotocum Pythium spinosum 15 [0157] In various additional embodiments wherein the crop plant is soybean, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 5, and the disease may be the corresponding disease of wheat listed in the left column of Table 5.

20 Table 5. Fungal diseases of soybean. Disease Causative fungal pathogen(s) Alternaria leaf spot Alternaria spp. Colletotrichum truncatum 25 Colletotrichum dematium f. truncatum Anthracnose Glomerella glycines Colletotrichum destructivum [anamorph] Black leaf blight Arkoola nigra 30 Thielaviopsis basicola Black root rot Chalara elegans [synanamorph] Septoria glycines Brown spot Mycosphaerella usoenskajae [teleomorph] 35 Phialophora gregata Brown stem rot = Cephalosporium gregatum Charcoal rot Macrophomina phaseolina Choanephora infundibulifera 40 Choanephora leaf blight Choanephora trispora Rhizoctonia solani Thanatephorus cucumeris [teleomorph] Pythium aphanidermatum 45 Damping-off Pythium debaryanum Pythium irregulare Pythium myriotylum Pythium ultimum 50 Downy mildew Peronospora manshurica Drechslera blight Drechslera glycines Frogeye leaf spot Cercospora sojina Fusarium root rot Fusarium spp. 55 Leptosphaerulina leaf spot Leptosphaerulina trifolii Mycoleptodiscus root rot Mycoleptodiscus terrestris

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(continued)

Disease Causative fungal pathogen(s) Neocosmospora vasinfecta 5 Neocosmospora stem rot Acremonium spp. [anamorph] Phomopsis seed decay Phomopsis spp. Phytophthora root and stem rot Phytophthora sojae

10 Phyllosticta leaf spot Phyllosticta sojaecola Phymatotrichopsis omnivora Phymatotrichum root rot = cotton root rot = Phymatotrichum omnivorum Diaporthe phaseolorum Pod and stem blight 15 Phomopsis sojae [anamorph] Powdery mildew Microsphaera diffusa Purple seed stain Cercospora kikuchii Pyrenochaeta leaf spot Pyrenochaeta glycines 20 Pythium aphanidermatum Pythium debaryanum Pythium rot Pythium irregulare Pythium myriotylum 25 Pythium ultimum Cylindrocladium crotalariae Red crown rot Calonectria crotalariae [teleomorph] Dactuliochaeta glycines Red leaf blotch = Dactuliophora leaf spot 30 = Pyrenochaeta glycines Dactuliophora glycines [synanamorph] Rhizoctonia solani Rhizoctonia aerial blight Thanatephorus cucumeris [teleomorph] 35 Rhizoctonia root and stem rot Rhizoctonia solani Rust Phakopsora pachyrhizi Scab Spaceloma glycines Sclerotinia stem rot Sclerotinia sclerotiorum 40 Sclerotium rolfsii Southern blight (damping-off and stem rot) = Sclerotium blight Athelia rolfsii [teleomorph] Diaporthe phaseolorum

45 Stem canker Diaporthe phaseolorum var. caulivora Phomopsis phaseoli [anamorph] Stemphylium botryosum Stemphylium leaf blight Pleospora tarda [teleomorph]

50 Sudden death syndrome Fusarium solani f.sp. glycines Target spot Corynespora cassiicola Yeast spot Nematospora coryli

55 [0158] In various additional embodiments wherein the crop plant is potato, the fungal pathogen may be any one of the fungal pathogens listed in the right hand column of Table 6, and the disease may be the corresponding disease of wheat listed in the left column of Table 6.

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Table 6. Fungal diseases of potato. Disease Causative fungal pathogen(s)

5 Colletotrichum coccodes Black dot = Colletotrichum atramentarium Alternaria alternata Brown spot and Black pit = Alternaria tenuis

10 Mycovellosiella concors = Cercospora concors Cercospora leaf blotch Cercospora solani Cercospora solani-tuberosi Macrophomina phaseolina 15 Charcoal rot = Sclerotium bataticola Choanephora blight Choanephora cucurbitarum Common rust Puccinia pittieriana 20 Deforming rust Aecidium cantensis Early blight Alternaria solani Fusarium spp. Gibberella pulicaris 25 = Fusarium solani Other Fusarium spp. include: Fusarium avenaceum Fusarium dry rot Fusarium oxysporum Fusarium culmorum 30 Less common Fusarium spp. include: Fusarium acuminatum Fusarium equiseti Fusarium croolcwellense 35 Fusarium spp. Fusarium avenaceum Fusarium wilt Fusarium oxysporum Fusarium solani f.sp. eumartii 40 Phoma solanicola f. foveata Phoma foveata Gangrene = Phoma exigua var. foveata = Phoma exigua f. sp. foveata Phoma exigua var. exigua 45 Botrytis cinerea Gray mold Botryotinia fuckeliana [teleomorph] Late blight Phytophthora infestans

50 Pythium spp. Pythium ultimum var. ultimum Leak = Pythium debaryanum Pythium aphanidermatum Pythium deliense 55 Phoma leaf spot Phoma andigena var. andina

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(continued)

Disease Causative fungal pathogen(s) Phytophthora spp. 5 Phytophthora cryptogea Phytophthora drechsleri Pink rot Phytophthora erythroseptica Phytophthora megasperma 10 Phytophthora nicotianae var. parasitica Powdery mildew Erysiphe cichoracearum Powdery scab Spongospora subterranea f.sp. subterranea Rhizoctonia solani Rhizoctonia canker and black scurf 15 Thanatephorus cucumeris [teleomorph] Rosellinia sp. Rosellinia black rot Dematophora sp. [anamorph] Septoria leaf spot Septoria lycopersici var. malagutii 20 Silver scurf Helminthosporium solani Skin spot Polyscytalum pustulans Sclerotium rolfsii Stem rot (southern blight) 25 Athelia rolfsii [teleomorph] Angiosorus solani Thecaphora smut = Thecaphora solani Ulocladium blight Ulocladium atrum 30 Verticillium albo-atrum Verticillium wilt Verticillium dahliae Wart Synchytrium endobioticum White mold Sclerotinia sclerotiorum 35

[0159] Various alternative embodiments and examples of the invention are described herein. These embodiments and examples are illustrative, and not limiting. [0160] Various implementations and examples of the combinations are described herein. These implementations and examples are illustrative, and not limiting. 40

EXAMPLES

Example 1: Greenhouse Stem Rust Evaluation Study

45 [0161] The efficacy of Civitas™ alone or in combination with Harmonizer™ in controlling infection of wheat (Triticum aestivum ’Norin43’) by Puccinia graminis f.sp. tritici ("Pgt") was tested under greenhouse conditions. Only the combination of Civitas™ with Harmonizer™ is according to the invention, the use of Civitas™ and Harmonizer™ alone are for reference purposes only. Briefly, each treatment consisted of four pots containing four plants. Plants were planted on March 2, 2011. Civitas™, Harmonizer™, and combinations thereof were applied to test plants, by foliar application or 50 soil drench, on March 10, 2011, seven days before inoculation (DBI) on March 17, 2011as indicated in Table 7. The average severity of infection, in terms of % leaf area infected, was evaluated 12 days after inoculation on March 29, 2011.

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Example 2: South Dakota State University Wheat Stem Rust Study

45 [0162] The efficacy of Civitas™ alone or in combination with Harmonizer™, Folicur™, or Quilt™ in controlling infection of wheat (Triticum aestivum ’Norin43’) by Pgt was tested between May and July 2010 at the South Dakota State University Plant Pathology Farm in Brookings, SD. Only the combination of Civitas™ with Harmonizer™, optionally with Folicur™ or Quilt™, is according to the invention, the use of Civitas™ and Harmonizer™ alone is for reference purposes only. A field was treated with Roundup™ on May 9, 2010 and cultivated twice before planting. Plots were planted on May 28, 50 2010 using a seeding rate of 84.74 kg/ha (1.25 bu/A), and were 4.5 m long (15 ft) by 1.5 m wide with 7 rows. Due to flooding in the field shortly after planting, plots lengths were reduced to 2.1 m long prior to cutting of the alleys. Plots consisting of a highly susceptible rust spreader mixture were alternated with the experimental units. [0163] The experimental design was a randomized complete block with five replicates. Puma™ (0.45 1/ha) and Bronate Advanced™ (0.941/ha) were applied on June 10, 2010 to control weeds. On July 14, 2011, urediniospores of Pgt were 55 collected from nearby trap plots and applied to the spreader rows in a 0.1% water agar suspension using a hand-powered backpack sprayer. On July 20, 2010, fungicide treatments were applied with a CO2-powered backpack sprayer in a carrier volume of 186 l/ha (20 gal/A) using XR8002 flat fan nozzles and an application pressure of 40 PSI. The plants in each plot were at Feekes 10.51 (early anthesis). At 48 hr after fungicide application, the experimental plots were

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inoculated as previously described with Pgt and misted at night for 7 days (3 min on per each 30 min) to facilitate infection and disease development. One treatment received a second application 7 days later (Treatement 5, see Table 8 below). Plots were rated for stem rust severity at 14 d after inoculation by visually estimating the percentage of stem area covered with pustules for 50 plants per plot (5 randomly chosen locations of 10 plants each). Plots were harvested with a small 5 plot combine and yield was determined. Data were analyzed using an ANOVA and pair-wise comparisons were performed using Tukey’s HSD (P=0.05).

Table 8. Results of South Dakota State University Wheat Stem Rust Study Upper Stem Average Stem rt Yield (g/ Yield (% of 10 App Rate (l/ha Severity (% Severity (% infected No. plot) Control) infected area) area) Non-inoculated Control 37.50 39.17 67.325 6 Inoculated Control 38.00 39.00 63.4 0 15 Civitas (11.68) 27.25 29.33 80.05 26 Civitas23.36) 25.75 28.50 63.475 0 Civitas + Harmonizer 26.25 29.50 71.65 13 (11.68+0.73) (1 app) 20 Civitas + Harmonizer 27.00 29.75 96.225 52 (11.68+0.73) (2 apps) Civitas + Harmonizer 25.50 30.00 78.525 24 (23.36+1.46) 25 Folicur (0.29) 25.00 29.08 142.175 124 Quilt (1.02) 14.50 19.17 161.75 155 0 Civitas + 1/2 Folicur 20.75 24.75 169.75 168 30 (11.68+0.15) 1 Civitas + Harmonizer + 1/2 19.25 24.25 176.2 178 Folicur (5.8+0.37+0.15) 2 Civitas + Harmonizer + 1/2 16.75 22.17 203.5 221

35 Folicur (11.68+0.73+0.15) 3 Civitas + Harmonizer + 1/2 11.00 16.92 185.175 192 Folicur (23.36+1.46+0.15) 4 Civitas + Harmonizer + 1/2 19.50 25.00 162.075 156 Quilt (5.8+0.37+0.51) 40

Example 3: Greenhouse Spot Blotch Evaluation Study

[0164] The efficacy of Civitas™/Harmonizer™, alone or in combination with Folicur™ in controlling infection of wheat 45 (Triticum aestivum ’Baart’) by Bipolaris sorokiniana was tested under greenhouse conditions. Only the combination of Civitas™ with Harmonizer™,optionally with Folicur™, is according to the invention, the use of Civitas™ and Harmonizer™ alone is for reference purposes only. Briefly, each treatment consisted of three pots (1.2 m x 1.2 m)(4" x 4") containing three plants each. Plants were planted on March 1, 2011. Civitas™/Harmonizer™, Folicur™, and combinations thereof were applied to test plants, by foliar application on March 8 (seven DBI), by soil drench on March 8, 2011 (7 DBI), or by 50 foliar application on March 14, 2011 (1 DBI), as indicated in Table 9 (rates of Civitas, Harmonizer, and Folicur are expressed in L/ha). For foliar application, the treaments were applied in 0.2 mL per pot, which is the equivalent of 186 l/ha (20 gal/A). For soil drench, treatments were applied in 3.8 mL, which is the equivalent of 3720 l/ha (400 gal/A). Plants were innoculated on March 15, 2011. The average severity of infection, in terms of % leaf area infected, was evaluated 14 days after inoculation on March 29, 2011. 55 [0165] Images of the untreated, inoculated control are presented in Figure 1. Note the number of pustules (dark spots), near lack of chlorosis (light halos surrounding dark spots), and large pustule size. Figure 2 shows leaves of inoculated plants that were treated with Civitas™/Harmonizer™ (11.68+0.73 L/ha) and Folicur (0.15 l/ha) by foliar application 7DBI.

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Note the near lack of symptoms, small pustule size, and chlorotic halos. Figure 3 shows leaves of inoculated plants that were treated with Civitas™/Harmonizer™ (23.36+1.46 l/ha) by soil drench application 7 DBI. Note the near lack of symptoms, chlorotic halos, and reduced pustule size.

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Example 4: Greenhouse Leaf Rust Evaluation Study

[0166] The efficacy of Civitas™/Harmonizer™, alone or in combination with Folicur™ in controlling infection of wheat (Triticumaestivum ’Baart’) by Puccinia triticina was testedunder greenhouse conditions.Only thecombination of Civitas™ 5 with Harmonizer™,optionally with Folicur™, is according to the invention, the use of Civitas™ and Harmonizer™ alone is for reference purposes only. Briefly, each treatment consisted of three pots (1.2 m by 1.2m) containing three plants each. Plants were planted on March 1, 2011. Civitas™/Harmonizer™, Folicur™, and combinations thereof were applied to test plants, by foliar application on March 8 (seven DBI), by soil drench on March 8, 2011 (7 DBI), or by foliar application on March 14, 2011 (1 DBI), as indicated in Table 10 (rates of Civitas, Harmonizer, and Folicur are expressed inl/ha). 10 For foliar application, the treaments were applied in 0.2 mL per pot, which is the equivalent of 186 l/ha (20 gal/A). For soil drench, treatments were applied in 3.8 mL, which is the equivalent of 3720 l/ha (400 gal/A). Plants were innoculated on March 15, 2011. The average severity of infection, in terms of % leaf area infected, was evaluated 14 days after inoculation on March 29, 2011.

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[0167] Images of the untreated, inoculated control are presented in Figure 4. Note the large number of pustules (dark spots), near lack of chlorosis, and large pustule size. Figure 5 shows leaves of inoculated plants that were treated with Civitas™/Harmonizer™ (11.68+0.73 l/ha) and Folicur (0.15 1/ha) by foliar application 7DBI. Note Note the near lack of pustules, somewhat restricted size, and small chlorotic halos indicative of a resistance response. Figure 6 shows leaves 5 of inoculated plants that were treated with Civitas™/Harmonizer™ (23.36+1.46 l/ha) by soil drench application 7 DBI. Note the lack of pustules, restricted size, and large chlorotic halos indicative of a resistance response.

Example 5: Greenhouse Fusarium Head Blight Evaluation Study

10 [0168] The efficacy of Civitas™, Harmonizer™, and Folicur™ alone or in combination, in controlling infection of wheat (Triticum aestivum ’Sonalika’) by Fusarium graminearum was tested under greenhouse conditions. Only the combination of Civitas™ with Harmonizer™, optionally with Folicur™, is according to the invention, the use of Civitas™ and Harmo- nizer™ alone is for reference purposes only. Briefly, each treatment consisted of four pots (1.2 m x 1.2 m) (4" x 4") containing nine plants each. Plants were planted on March 2, 2011. Civitas™, Harmonizer™, Folicur™, and combinations 15 thereof were applied to test plants, by foliar application or by soil drench on March 10 (39 DBI), or 35 DBI by foliar application on March 16, 2011, as indicated in Table 11 (rates of Civitas, Harmonizer, and Folicur are expressed in 1/ha). For foliar application, the treaments were applied in 0.2 mL per pot, which is the equivalent of 186 l/ha (20 gal/A). For soil drench, treatments were applied in 3.8 mL, which is the equivalent of 3720 l/ha (400 gal/A). Plants were innoculated on April 18, 2011. The average severity of infection was evaluated 14 days after inoculation on May 2, 2011. 20

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Example 6. Control of Leaf rust on wheat

[0169] Leaf rust field trial was carried out on spring wheat cultivars. Spores from the spreader plots were served as 50 innoculum source for the natural infection of experimental plots. Treatments were applied at heading (Feekes 10.1/10.2) using a CO2-powered backpack sprayer operating at the pressure of ca. 276 kPa, fitted with flat-fan spray tip (TeeJet SS8003; Spraying Systems Co., Wheaton, IL), at the rate of 1861/ha (20 gal/acre). Prosaro (Bayer Crop Science) was used as the standard chemical control. [0170] Disease rating was done 19 days after chemical spray. Leaf rust severity was rated as percent leaf area infected 55 on 12 randomly selected flag leaves per plot. Data were analyzed using ’R’ statistical package. Data on leaf rust severity was transformed using square root and arcsin function for analysis of variance. Means presented for rust severity in the graph and tables are back transformed mean value.

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[0171] The treatments of Civitas/Harmonizer (11.68:0.73 l/ha) and Civitas/Harmonizer (23.36:1.46 l/h) resulted in significantly low rust infection compared to control plots. The efficacy of Civitas treatments are at par with the chemical standard Prosaro (0.47 1/ha).

5 ANOVA table (Table 12): Source DF MS F-value Prob > F Treatment 12 6.199 2.617 0.01157 Error 39 2.3686 ...... 10

Table 13. Mean Comparisons Between Treatments: Treatment Mean Group* 15 Untreated 2.81 a Civitas/Harmonizer - 11.68:0.73 l/ha 0.88 b Prosaro - 0.47 l/ha (reference example) 0.77 b

20 Civitas/Harmonizer - 23.36:1.46 l/ha 0.67 b *Treatment with same letters are not statistically different

Example 7. Control of Gray Leaf Spot on Corns 25 [0172] Gray Leaf Spot (Cercospora zeae-maydis) field trial was conducted on hybrid corns (NK 67 3000GT) with natural infection. Civitas treatments were applied at R1 and R3 growth stage with the spray rate of 186 1/ha. Headline (BASF) and Stratego (Bayer Crop Science) were applied at R1 as the standard chemical control. [0173] Disease rating was done about 16 days and 40 days after R1 application. Gray leaf spot severity was rated as 30 percent leaf area infected in the plots. [0174] All of the chemical treatments resulted in lower disease severity than control plots.

Table 14 16D 40DA 35 AA A No of application Growth % Leaf area % Leaf area treatment Chemicals rate Stage infected infected untreated 2.5 A 12.0 40 1 Civitas 46.72 R1 + R3 1.0 C 7.8 +Harmonizer 2.92 2 Headline (ref.) 0.44 R1 1.0 C 0.8

45 3 Stratego (ref.) 0.73 R1 1.0 C 1.0 P>F 0.0084 <.0001 LSD 0.05 0.9 4.2 CV% 46 73

Claims

1. Use of a fungicidal composition comprising a paraffinic oil-in-water emulsion, the paraffinic oil-in-water emulsion comprising a paraffinic oil, an emulsifier, a pigment and a silicone surfactant, for controlling infection of a crop plant 55 by a fungal pathogen, wherein the pigment is a copper phthalocyanine and wherein:

the ratio of the paraffinic oil to the pigment is from 5:1 to 100:1;

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the weight ratio of the paraffinic oil to the emulsifier is from 10:1 to 500:1; and the weight ratio of the pigment to the silicone surfactant is from 2:1 to 50:1.

2. The use according to claim 1, wherein the crop plant is wheat, barley, soybean, or corn. 5 3. The use according to claim 1 or claim 2, wherein the plant is monocotyledonous.

4. The use according to claim 3, wherein the plant is of the order Poaceae.

10 5. The use according to claim 4, wherein the plant is of the genus Triticum, Secale, Hordeum, Oryza, Zea, or Elymus.

6. The use according to any one of claims 1 to 5, wherein the fungal pathogen is of the order Pucciniales.

7. The use according to claim 6, wherein the fungal pathogen is of the genus Puccinia. 15 8. The use according to claim 7, wherein the fungal pathogen is of the species Puccinia graminis, Puccinia triticina, or Puccinia striiformis.

9. The use according to any one of claims 1 to 5, wherein the fungal pathogen is selected from the group consisting 20 of Bipolaris sorokiniana, Fusarium graminearum, and Pyrenophora triticirepentis.

10. The use according to claim 1 or claim 2, wherein the plant is dicotyledonous.

11. The use according to claim 10, wherein the plant is of the order Fabaceae. 25 12. The use according to claim 11, wherein the plant is of the species Glycine max.

13. The use according to any one of claims 10 to 12, wherein the fungal pathogen is of the genus Phakopsora.

30 14. The use according to claim 13, wherein the fungal pathogen is Phakopsora pachyrhizi or Phakopsora meibomiae.

15. The use according to claim 10, wherein the plant is of the genus Gossypium.

16. The use according to claim 15, wherein the fungal pathogen is Phakopsora gossypii. 35 17. The use according to claim 10, wherein the fungal pathogen is Phytophthora infestans.

18. The use according to any one of claims 1 to 17, wherein the paraffinic oil comprises a paraffin having a number of carbon atoms ranging from 12 to 50. 40 19. The use according to any one of claims 1 to 18, wherein the paraffinic oil has a paraffin content of at least 80%.

20. The use according to any one of claims 1 to 19, wherein the paraffinic oil used in a range of 71.4 g/ha to 228.6 kg/ha (1 to 3200 oz/acre). 45 21. The use according to any one of claims 1 to 20, wherein the fungicidal composition further comprises a demethylation inhibitor (DMI).

22. The use according to claim 21, wherein the DMI is tetraconazole, tebuconazole, propioconazole, azaconazole, 50 bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, prothioconazole, simeconazole, triadimefon, triadimenol, triticonazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole, fenarimol, nuarimol, triforine, or pyrifenox.

55 23. The use according to any one of claims 1 to 22, wherein the fungicidal composition further comprises a Quinone outside Inhibitor (QoI).

24. The use according to claim 23, wherein the QoI is azoxystrobin, enestrobin, picoxystrobin, pyraclostrobin, trifloxys-

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trobin, dimoxystrobin, metominostrobin, orysastrobin, famoxadonem, fluoxastrobin, fenamidone, or pyribencarb.

25. The use according to claim 1, wherein the pigment is a polychlorinated Cu II phthalocyanine.

5 26. The use according to any one of claims 21 to 24, wherein the weight ratio of the paraffinic oil to the demethylation inhibitor is from 2:1 to 10000:1.

Patentansprüche 10 1. Verwendung einer eine paraffinische Öl-in-Wasser-Emulsion umfassenden fungiziden Zusammensetzung, wobei die paraffinische Öl-in-Wasser-Emulsion ein paraffinisches Öl, einen Emulgator, ein Pigment und ein Silicontensid umfasst, zur Bekämpfung einer Infektion einer Kulturpflanze durch ein pilzliches Pathogen, wobei es sich bei dem Pigment um Kupferphthalocyanin handelt und wobei: 15 das Verhältnis von paraffinischem Öl zum Pigment 5:1 bis 100:1 beträgt, das Gewichtsverhältnis von paraffinischem Öl zum Emulgator 10:1 bis 500:1 beträgt und das Gewichtsverhältnis von Pigment zum Silicontensid 2:1 bis 50:1 beträgt.

20 2. Verwendung nach Anspruch 1, wobei es sich bei der Kulturpflanze um Weizen, Gerste, Sojabohne oder Mais handelt.

3. Verwendung nach Anspruch 1 oder Anspruch 2, wobei die Pflanze monokotyledon ist.

4. Verwendung nach Anspruch 3, wobei die Pflanze aus der Ordnung Poaceae stammt. 25 5. Verwendung nach Anspruch 4, wobei die Pflanze aus der Gattung Triticum, Secale, Hordeum, Oryza, Zea oder Elymus stammt.

6. Verwendung nach einem der Ansprüche 1 bis 5, wobei das pilzliche Pathogen aus der Ordnung Pucciniales stammt. 30 7. Verwendung nach Anspruch 6, wobei das pilzliche Pathogen aus der Gattung Puccinia stammt.

8. Verwendung nach Anspruch 7, wobei es sich bei dem pilzlichen Pathogen um die Art Puccinia graminis, Puccinia triticina oder Puccinia striiformis handelt. 35 9. Verwendung nach einem der Ansprüche 1 bis 5, wobei das pilzliche Pathogen aus der aus Bipolaris sorokiniana, Fusarium graminearum und Pyrenophora triticirepentis bestehenden Gruppe ausgewählt ist.

10. Verwendung nach Anspruch 1 oder Anspruch 2, wobei die Pflanze dikotyledon ist. 40 11. Verwendung nach Anspruch 10, wobei die Pflanze aus der Ordnung Fabaceae stammt.

12. Verwendung nach Anspruch 11, wobei es sich bei der Pflanze um die Art Glycine max handelt.

45 13. Verwendung nach einem der Ansprüche 10 bis 12, wobei das pilzliche Pathogen aus der Gattung Phakopsora stammt.

14. Verwendung nach Anspruch 13, wobei es sich bei dem pilzlichen Pathogen um Phakopsora pachyrhizi oder Pha- kopsora meibomiae handelt. 50 15. Verwendung nach Anspruch 10, wobei die Pflanze aus der Gattung Gossypium stammt.

16. Verwendung nach Anspruch 15, wobei es sich bei dem pilzlichen Pathogen um Phakopsora gossypii handelt.

55 17. Verwendung nach Anspruch 10, wobei es sich bei dem pilzlichen Pathogen um Phytophthora infestans handelt.

18. Verwendung nach einem der Ansprüche 1 bis 17, wobei das paraffinische Öl ein Paraffin mit einer Kohlenstoffa- tomanzahl im Bereich von 12 bis 50 umfasst.

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19. Verwendung nach einem der Ansprüche 1 bis 18, wobei das paraffinische Öl einen Paraffingehalt von mindestens 80% aufweist.

20. Verwendung nach einem der Ansprüche 1 bis 19, wobei das paraffinische Öl in einem Bereich von 71,4 g/ha bis 5 228,6 kg/ha (1 bis 3200 oz/acre) eingesetzt wird.

21. Verwendung nach einem der Ansprüche 1 bis 20, wobei die fungizide Zusammensetzung weiterhin einen Deme- thylierungsinhibitor (DMI) umfasst.

10 22. Verwendung nach Anspruch 21, wobei es sich bei dem DMI um Tetraconazol, Tebuconazol, Propiconazol, Azaco- nazol, Bitertanol, Bromuconazol, Cyproconazol, Difenoconazol, Diniconazol, Epoxiconazol, Etaconazol, Fenbuco- nazol, Fluquinconazol, Flusilazol, Flutriafol, Hexaconazol, Imibenconazol, Ipconazol, Metconazol, Myclobutanil, Penconazol, Prothioconazol, Simeconazol, Triadimefon, Triadimenol, Triticonazol, Imazalil, Oxpoconazol, Pefura- zoat, Prochloraz, Triflumizol, Fenarimol, Nuarimol, Triforin oder Pyrifenox handelt. 15 23. Verwendung nach einem der Ansprüche 1 bis 22, wobei die fungizide Zusammensetzung weiterhin einen Quinone- Outside-Inhibitor (QoI) umfasst.

24. Verwendung nach Anspruch 23, wobei es sich bei dem QoI um Azoxystrobin, Enestrobin, Picoxystrobin, Pyraclos- 20 trobin, Trifloxystrobin, Dimoxystrobin, Metominostrobin, Orysastrobin, Famoxadon, Fluoxastrobin, Fenamidon oder Pyribencarb handelt.

25. Verwendung nach Anspruch 1, wobei es sich bei dem Pigment um polychloriertes Cu II-Phthalocyanin handelt.

25 26. Verwendung nach einem der Ansprüche 21 bis 24, wobei das Gewichtsverhältnis von paraffinischem Öl zum De- methylierungsinhibitor 2:1 bis 10000:1 beträgt.

Revendications 30 1. Utilisation d’une composition fongicide comprenant une émulsion paraffinique huile-dans-eau, l’émulsion paraffinique huile-dans-eau comprenant une huile paraffinique, un émulsifiant, un pigment et un tensioactif de type silicone, pour la lutte contre l’infection d’une plante de culture par un pathogène fongique, le pigment étant de type phtalocyanine de cuivre et : 35 le rapport d’huile paraffinique à pigment étant de 5 : 1 à 100 : 1 ; le rapport pondéral d’huile paraffinique à émulsifiant étant de 10 : 1 à 500 : 1 ; le rapport pondéral de pigment à tensioactif de type silicone étant de 2 : 1 à 50 : 1.

40 2. Utilisation selon la revendication 1, la plante de culture étant le blé, l’orge, le soja ou le maïs.

3. Utilisation selon la revendication 1 ou la revendication 2, la plante étant une monocotylédone.

4. Utilisation selon la revendication 3, la plante étant de l’ordre des Poaceae. 45 5. Utilisation selon la revendication 4, la plante étant du genre Triticum, Secale, Hordeum, Oryza, Zea ou Elymus.

6. Utilisation selon l’une quelconque des revendications 1 à 5, le pathogène fongique faisant partie de l’ordre des Pucciniales. 50 7. Utilisation selon la revendication 6, le pathogène fongique étant du genre Puccinia.

8. Utilisation selon la revendication 7, le pathogène fongique étant de l’espèce Puccinia graminis, Puccinia triticina ou Puccinia striiformis. 55 9. Utilisation selon l’une quelconque des revendications 1 à 5, le pathogène fongique étant choisi dans le groupe constitué par Bipolaris sorokiniana, Fusarium graminearum et Pyrenophora triticirepentis.

41 EP 2 713 749 B1

10. Utilisation selon la revendication 1 ou la revendication 2, la plante étant une dicotylédone.

11. Utilisation selon la revendication 10, la plante faisant partie de l’ordre des Fabaceae.

5 12. Utilisation selon la revendication 11, la plante étant de l’espèce Glycine max.

13. Utilisation selon l’une quelconque des revendications 10 à 12, le pathogène fongique étant du genre Phakopsora.

14. Utilisation selon la revendication 13, le pathogène fongique étant Phakopsora pachyrhizi ou Phakopsora meibomiae. 10 15. Utilisation selon la revendication 10, la plante étant du genre Gossypium.

16. Utilisation selon la revendication 15, le pathogène fongique étant Phakopsora gossypii.

15 17. Utilisation selon la revendication 10, le pathogène fongique étant Phytophthora infestans.

18. Utilisation selon l’une quelconque des revendication 1 à 17, l’huile paraffinique comprenant une paraffine présentant un nombre d’atomes de carbone dans la plage de 12 à 50.

20 19. Utilisation selon l’une quelconque des revendications 1 à 18, l’huile paraffinique ayant une teneur en paraffine d’au moins 80%.

20. Utilisation selon l’une quelconque des revendications 1 à 19, l’huile paraffinique étant utilisée dans la plage de 71,4 g/ha à 228,6 kg/ha (1 à 3200 oz/acre). 25 21. Utilisation selon l’une quelconque des revendications 1 à 20, la composition fongicide comprenant en outre un inhibiteur de la déméthylation (IDM).

22. Utilisation selon la revendication 21, le DMI étant le tétraconazole, le tébuconazole, le propioconazole, l’azaconazole, 30 le bitertanol, le bromuconazole, le cyproconazole, le difénoconazole, le diniconazole, l’époxiconazole, l’étaconazole, le fenbuconazole, le fluquinconazole, le flusilazole, le flutriafol, l’hexaconazole, l’imibenconazole, l’ipconazole, le metconazole, le myclobutanil, le penconazole, le prothioconazole, le siméconazole, le triadiméfon, le triadiménol, le triticonazole, l’imazalil, l’oxpoconazole, le pefurazoate, le prochloraz, le triflumizole, le fénarimol, le nuarimol, la triforine ou le pyrifénox. 35 23. Utilisation selon l’une quelconque des revendications 1 à 22, la composition fongicide comprenant en outre un inhibiteur externe de la quinone (QoI).

24. Utilisation selon la revendication 23, le QoI étant l’azoxystrobine, l’énestrobine, la picoxystrobine, la pyraclostrobine, 40 la trifloxystrobine, la dimoxystrobine, la métominostrobine, l’orysastrobine, le famoxadonem, la fluoxastrobine, la fénamidone ou le pyribencarb.

25. Utilisation selon la revendication 1, le pigment étant de type phtalocyanine de Cu II polychlorée.

45 26. Utilisation selon l’une quelconque des revendications 21 à 24, le rapport pondéral d’huile paraffinique à inhibiteur de la déméthylation étant de 2 : 1 à 10.000 : 1.

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

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