Fungicidal compositions

Abstract

A fungicidal suspension concentrate composition, comprising: (i) 25 to 35% by weight of sulfur; (ii) 1 to 5% by weight of difenoconazole; (iii) 2.0 to 4.5% by weight of a styrene acrylic acid copolymer, or a salt thereof; and (iv) 0.5 to 2.5% by weight of a fumed silica material.

Description

[0001] 109861_FF (83097)

[0002] Fungicidal compositions

[0003] The present invention relates to a fungicidal composition, in particular to a suspension concentrate composition comprising difenoconazole and sulfur as fungicidal active ingredients, to the preparation thereof, to aqueous compositions prepared from the suspension concentrate, and to a method of using such an aqueous composition to control fungal pathogens in crops of useful plants.

[0004] Difenoconazole (CAS no.: 119446-68-3) is a fungicide with a broad range of activity used as a spray or seed treatment. Sulfur (CAS no.: 7704-34-9) is a fungicidal agent that has been in use for many years, and which is normally used in powdered form. WO 2012 / 101660 discloses a wettable granule (WG) formulation comprising 65% by weight of sulfur to 15% by weight of difenoconazole.

[0005] Suspension concentrate formulations consist of a solid (insoluble) active ingredient(s) dispersed in water, and may be desirable compared to other formulation types (eg, wettable granules (WG) and wettable powders (WP)) because of the absence of the generation of dust during handling, and their general ease of use and effectiveness.

[0006] Particular challenges may arise when formulating active ingredient mixtures of sulfur as a suspension concentrate for agrochemical purposes (with or without the presence of other active ingredients) due to the relatively high density of sulfur (approximately 2.07 g / cm3). Serum separation and the sedimentation of the components are frequently observed over time, resulting in a sub-optimal formulation or indeed a formulation unfit for use. Accordingly, there remains a strong motivation to develop novel stable suspension concentrate formulations comprising sulfur in combination with other active ingredients, such as difenoconazole, where any issues of serum separation and sedimentation are substantially remedied.

[0007] According to the present invention, there is provided a fungicidal suspension concentrate composition, comprising:

[0008] (i) 25 to 35% by weight of sulfur;

[0009] (II) 1 to 5% by weight of difenoconazole;

[0010] (ill) 2.0 to 4.5% by weight of a styrene acrylic acid copolymer, or a salt thereof; and

[0011] (iv) 0.5 to 2.5% by weight of a fumed silica material.

[0012] The pesticidal compositions of the present invention have, for practical purposes, a very advantageous level of activity in controlling certain fungal pathogens in crops of useful plants after foliar application (suitable dilution of suspension concentrate), whilst also maintaining acceptable crop safety (phytotoxicity) outcomes. Additionally, the pesticidal compositions of the present invention with their specific combination of components possess excellent dilution properties and chemical stability, as well as good physical stability with low serum separation and low sediment formation compared to closely related variants. 109861_FF (83097)

[0013] Further according to the invention, there is provided an aqueous composition comprising the fungicidal suspension concentrate composition according to the invention, optionally further comprising one or more adjuvants or carriers.

[0014] Still further according to the invention, there is provided a (non-therapeutic) method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of aqueous composition according to the invention is applied to the plants, to parts thereof or the locus thereof.

[0015] Preferably, the crop of useful plant is rice, peanut, cumin, mango and soybean, and most preferably, rice.

[0016] Preferably, the phytopathogenic microorganism is selected from a fungal pathogen causing a plant disease including rice sheath blight (eg, Rhizoctonia solani), rice brown leaf spot (eg, Bipolaria oryzae), rice powdery mildew (eg, Blumeria graminis).

[0017] Percentage weights (% by weight) for the various components of the suspension concentrate composition are defined in accordance relative to the present invention by the total weight of the suspension concentrate composition up to a total of 100% by weight.

[0018] Preferably, the composition according to the present invention comprises 28 to 32% by weight of sulfur, and 2 to 3% by weight of difenoconazole.

[0019] The compositions of the present invention comprise a styrene acrylic acid copolymer, or a salt thereof (eg, a sodium salt), (eg, Atlox™ Metasperse 550S or Atlox™ 4971 (Croda Inc., USA)) as a dispersant. A dispersant or dispersing agent plays a crucial role in ensuring the proper dispersion and suspension of the solid active ingredient particles and other solid particles in a suspension concentrate composition. Preferably, the styrene acrylic acid copolymer is present at 3.5 to 4.5% by weight of the total weight of the suspension concentrate composition.

[0020] The compositions of the present invention comprise a fumed silica material (eg, Aerosil® R805, Aerosil® R202, Aerosil® R972, Aerosil® R974, Evonik Industries, Germany). A fumed silica may be described as a highly dispersed, amorphous silicon dioxide (SiC ) material that may be used as a rheology modifier, thickener and anti-settling agent in agrochemical formulations. Preferably, the fumed silica material is present at 0.5 to 1.5% by weight of the total weight of the suspension concentrate compositions. The fumed silica material may have a specific surface area (BET) in the range of 50 to 200 m2 / g, preferably 80 to 190 m2 / g, and more preferably 125 to 175 m2 / g.

[0021] It would appear that in accordance with the present invention, the specific combination of the styrene acrylic acid copolymer (or salt thereof) dispersant with the fumed silica material in conjunction with the specific loadings of the sulfur and difenoconazole active ingredients provides the beneficial 109861_FF (83097) physical properties that have been observed for the suspension concentrate compositions (see Examples below).

[0022] In certain embodiments of the compositions of the present invention, there may be included as a dispersant a naphthalenesulfonic acid, sodium salt condensed with formaldehyde (eg, Morwet® D425, Nouryon Surface Chemistry AB, Sweden. CAS no.: 68425-94-5 ((C-ioHsOsS^CF^OJn’xNa, Orotan™ SN Rohm & Haas, France). A naphthalenesulfonic acid, sodium salt condensed with formaldehyde may be present at 2.0 to 3.0% by weight, and preferably 1.5 to 1.75% by weight of the total weight of the suspension concentrate compositions.

[0023] In certain embodiments of the compositions of the present invention, there may be included as a dispersant a propylene-oxide / ethylene-oxide copolymer (eg, Pluronic PE 10500 or Pluronic PE 10400 (CAS no.: 9003-11-6), BASF, Germany). By way of example, the propylene-oxide / ethylene-oxide copolymer may be a triblock copolymer consisting of a central hydrophobic polypropylene oxide) (PPO) block flanked by two hydrophilic poly(ethylene oxide) (PEO) blocks. A propylene-oxide / ethylene-oxide copolymer may be present at 2.0 to 3.0% by weight of the total weight of the suspension concentrate compositions. Preferably, the propylene-oxide / ethylene-oxide copolymer has a molecular weight of 5,000 to 15,000 g / mol, and more preferably 6,000 to 12,000 g / mol.

[0024] In certain embodiments of the compositions of the present invention, there may be included as a dispersant a polyvinylpyrrolidone (eg, PVP K-90 or PVP K-30, Ashland, USA). A polyvinylpyrrolidone may be present at 1 .0 to 1 .4% by weight of the total weight of the suspension concentrate compositions.

[0025] In certain embodiments of the compositions of the present invention, there may be included as a dispersant a solution of an acrylic graft copolymer in water and propylene glycol, eg, Atlox™ 4913 (Croda Inc., USA), Zephrym PD 3315 (Croda Inc., USA). Such solution may be present at 0.5 to 1 .5 % by weight of the total weight of the suspension concentrate compositions.

[0026] An anti-freeze agent is a substance that may be added to pesticidal formulations to prevent damage or degradation caused by freezing and thawing cycles. Propylene glycol, ethylene glycol, and glycerol are widely used anti-freeze agents. Preferred is propylene glycol.

[0027] An anti-foaming agent is a chemical additive that reduces and hinders the formation of foam in a composition, such as a pesticidal formulation. Anti-foaming agents which may be used in accordance with the present invention include, but are not limited to, polydimethylsiloxanes (eg, Rhodorsil AF- 454,Elkem, France; XIAMETER™ ACP-1500, Dow, Inc; Antifoam MSA, Univar; Xiameter ACP-0001 , Dow Brasil; Xiameter ACP-0100, Dow Chemical; SAG™ 1572, Momentive Performance Materials Inc.).

[0028] A thickener may provide thickening and suspension properties to liquid formulations such as suspension concentrates. Examples may include Laponite EP (BYK Additives & Instruments, Germany), Attagel® 50 (BASF, Germany), which are synthetic clay minerals. 109861_FF (83097)

[0029] A biocide (preservative) is an additive to help the preservation of industrial water-based products against spoilage from bacteria, yeasts and fungi. Examples may include Proxel™ GXL (Arxada, Switzerland) or Acticide® L30 (Thor Group Limited, UK). Such biocidal products may comprise as active ingredient one or more of 2-methyl-4-isothiazolin-3-one, 1 ,2-benzisothiazolin-3-one and 5-chloro-2- methyl-4-isothiazolin-3-one.

[0030] In relation to the anti-freeze, anti-foaming and biocidal components, the amounts would be readily understood by the person skilled in the art.

[0031] Within the scope of the invention, useful plants to be protected typically comprise the following species of plants: cereal (such as for example wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (such as for example sugar beet and fodder beet); pomes, drupes and soft fruit (such as for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (such as for example beans, lentils, peas, soybeans); oil plants (such as for example rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (such as for example pumpkins, cucumbers, melons); fibre plants (such as for example cotton, flax, hemp, jute); citrus fruit (such as for example oranges, lemons, grapefruit, mandarins); vegetables and more particularly leafy vegetables (such as for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (such as for example avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

[0032] In a preferred embodiment, the plants can be selected among pomes, drupes and soft fruit (such as for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (such as for example beans, lentils, peas, soybeans); cucumber plants (such as for example pumpkins, cucumbers, melons); citrus fruit (such as for example oranges, lemons, grapefruit, mandarins); vegetables and more particularly leafy vegetables (such as for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); and pepper.

[0033] In practical usage, the suspension concentrate composition according to the present invention will undergo dilution (eg, with water in a tank) prior to a spray application to a crop by conventional techniques. Typical fungicidal active ingredient application rates (g / ha) of an aqueous composition according to the invention will be of the order of 40 to 60 g / ha for difenoconazole and 550 to 650 g / ha for sulfur. More preferred is 45 to 55 g / ha (eg, 50 g / ha) for difenoconazole and 580 to 620 g / ha (eg, 600 g / ha) for sulfur. In one embodiment of the method of the invention, the aqueous composition involves a dilution of approximately 2 kgs of the suspension concentrate of the invention for an overall application volume of 300 to 500 L / ha.

[0034] The aqueous compositions of the invention when prepared may be tank-mixed with an additional fungicidal active ingredient selected from benzovindiflupyr, isopyrazam, pydiflumetofen, azoxystrobin, prothioconazole, chlorothalonil, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, paclobutrazol, thiabendazole. 109861_FF (83097)

[0035] Compositions of the invention may be prepared in accordance with standard formulation methodologies known to the person skilled in the art. In terms of units used herein, g / ha refers to grams per hectare. L / ha refers to litres per hectare.

[0036] DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 : Sample storage containers (after 2 weeks at 54 °C). EXAMPLES

[0038] The Examples which follow serve to illustrate the invention, and in particular, demonstrate the physical stability of the compositions according to the present invention (see Table 1 below). The compositions of Comparative Example A (not according to the invention), Example 1 and Example 2 (both according to the invention) were prepared according to standard techniques and comprise equal levels of active ingredient loading.

[0039] Table 1: 109861_FF (83097)

[0040] The data in Table 1 clearly demonstrate the formulation stability of Examples 1 and 2 in accordance with the present invention by virtue of relatively low and acceptable serum formation of 15 and 12%, respectively (refer Figure 1), after two weeks sealed storage at a temperature of 54 °C compared to Comparative Example A with serum formation of approximately 35% under the same conditions.

[0041] To further demonstrate these outcomes, Figure 1 herein shows the relative serum separations (dark layer highlighted by parentheses) between equal volumes of the composition of Comparative Example A (not according to the invention) and Examples 1 and 2 (according to the invention) in a sample container of the same dimension.

Claims

109861_FF (83097)Claims:1 . A fungicidal suspension concentrate composition, comprising:(i) 25 to 35% by weight of sulfur;(II) 1 to 5% by weight of difenoconazole;(iii) 2.0 to 4.5% by weight of a styrene acrylic acid copolymer, or a salt thereof; and(iv) 0.5 to 2.5% by weight of a fumed silica material.

2. The composition according to claim 1 , comprising 28 to 32% by weight of sulfur.

3. The composition according to claim 1 or claim 2, comprising 2 to 3% by weight of difenoconazole.

4. The composition according to any one of claims 1 to 3, comprising 3.5 to 4.5% by weight of a styrene acrylic acid copolymer, or a salt thereof (eg, a sodium salt).

5. The composition according to any one of claims 1 to 4, comprising 0.5 to 1 .5% by weight of a fumed silica material.

6. The composition according to any one of claims 1 to 5, further comprising 1 .5 to 1 .75% by weight of naphthalenesulfonic acid, sodium salt condensed with formaldehyde.

7. The composition according to any one of claims 1 to 6, further comprising 2.0 to 3.0% by weight of a propylene-oxide / ethylene-oxide copolymer.

8. The composition according to any one of claims 1 to 7, further comprising 1 .0 to 1 .4% by weight of a polyvinylpyrrolidone.

9. The composition according to any one of claims 1 to 8, further comprising one or more additional ingredients selected from an anti-freeze agent, an anti-foam agent, a thickening agent, a biocide (preservative), a buffering agent, a stabilizer and / or a pigment.

10. An aqueous composition comprising the fungicidal suspension concentrate composition of any one of claims 1 to 9, optionally further comprising one or more adjuvants or carriers.

11. The aqueous composition of claim 10, further comprising an additional fungicidal active ingredient.

12. The aqueous composition of claim 11 , wherein the additional fungicidal active ingredient is selected from benzovindiflupyr, isopyrazam, pydiflumetofen, azoxystrobin, prothioconazole, chlorothalonil, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph,109861_FF (83097) propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, thiabendazole.

13. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of an aqueous composition according to any one of claims 10 to 12 is applied to the plants, to parts thereof or the locus thereof.

14. The method according to claim 13, wherein the useful plant is selected from rice, soybean, peanut, cumin, and mango, and preferably rice.

15. The method according to claim 13 or 14, wherein the phytopathogenic microorganism is selected from a fungal pathogen causing a plant disease including rice sheath blight (eg, Rhizoctonia solani), rice brown leaf spot (eg, Bipolaria oryzae), rice powdery mildew (eg, Blumeria graminis).

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