Formulations comprising fludioxonil

Abstract

The present invention relates to an aqueous composition comprising (a) at least 10% by weight, relative to the total weight of the composition, of fludioxonil, (b) at least one polyoxyalkylene copolymer having an average molecular weight of up to 4000 g / mol, (c) at least one dispersant, and (d) water.

Description

[0001] The present invention relates to a composition comprising fludioxonil. More particularly, the invention relates to formulations such as suspension concentrates (SC) or suspoemulsions (SE); to dilutions or dispersions of such formulations, more particularly in a farmer's spray tank; and to the use of such compositions in agriculture or horticulture for controlling or preventing infection of plants by phytopathogenic microorganisms, preferably fungi.

[0002] Fludioxonil is a fungicidal agrochemical commercially available in different dosage forms. When high loadings of fludioxonil are required, there are not many solutions on the market. Although water dispersible granules exist, this solid formulation suffers from dusting problems and requires careful handling. In addition, this solid formulation does not exhibit satisfactory retention properties.

[0003] The object of the present invention is to overcome the problems of the prior art by proposing a composition comprising a high loading of fludioxonil which improves the retention properties while ensuring satisfactory sprayability conditions.

[0004] To this end, the object of the present invention is to provide an aqueous composition comprising:

[0005] (a) at least 10% by weight of fludioxonil relative to the total weight of the composition,

[0006] (b) at least one polyoxyalkylene copolymer having an average molecular weight of up to 4000 g / mol,

[0007] (c) at least one dispersant, and

[0008] (d) Water.

[0009] Thanks to the aqueous composition of the present invention, all of the above problems have been overcome. More particularly, the present invention provides an aqueous composition having improved retention characteristics while ensuring low viscosity to ensure good handling and satisfactory sprayable conditions. In addition, due to the high loading of fludioxonil, a smaller amount of composition is required per hectare. Another significant advantage of the present invention is that the composition also exhibits good chemical and physical stability over time, especially when stored.

[0010] The composition of the present invention comprises at least one active ingredient which is fludioxonil. Fludioxonil is a fungicide having the following CAS number: 131341-86-1 and having the following chemical formula:

[0011]

[0012] Therefore, the aqueous composition according to the invention is more particularly a fungicidal composition.

[0013] The present invention may have a large amount of active ingredients, especially a large amount of fludioxonil, such as at least 10% by weight relative to the total weight of the composition. More particularly, the composition may contain 20% to 60% by weight of fludioxonil, preferably 30% to 50% by weight of fludioxonil, and more preferably 35% to 45% by weight of fludioxonil relative to the total weight of the composition.

[0014] The composition may comprise one or several polyoxyalkylene copolymers (b) having an average molecular weight of up to 4000 g / mol, preferably up to 3000 g / mol, preferably from 2000 to 3000 g / mol, preferably from 2100 to 3000 g / mol and more preferably from 2200 to 2700 g / mol.

[0015] In the present invention, the expression "average molecular weight of" means "a molecular weight of about". The molecular weight, or in other words the molar mass, of a polymer can be easily determined by methods well known in the art, such as gel permeation chromatography (GPC).

[0016] The composition of the present invention may contain 1 to 30% by weight of the polyoxyalkylene copolymer (b), preferably 1 to 20% by weight of the polyoxyalkylene copolymer (b), and more preferably 5 to 10% by weight of the polyoxyalkylene copolymer (b), relative to the total weight of the composition.

[0017] In the present invention, the polyoxyalkylene copolymer can be obtained from at least two different alkylene oxides, such as ethylene oxide monomers and propylene oxide monomers. The common name of such polyoxyalkylene copolymers is propylene oxide and ethylene oxide copolymers.

[0018] The polyoxyalkylene copolymer may more preferably be an AB, ABA, BAB, or ABABA type polyoxyalkylene block copolymer.

[0019] More specifically, the polyoxyalkylene copolymers can be prepared by ring-opening polymerization of corresponding cyclic ethylene oxide monomers and propylene oxide monomers.

[0020] Typically, the ring-opening polymerization is initiated by the addition of water and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.The block structure of the copolymer is formed by first polymerizing a polymer block using one monomer and then adding a second monomer to form additional polymer blocks.

[0021] In a preferred embodiment, the polyoxyalkylene copolymer can be an ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO-PO-EO block copolymer), or in other words a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer or a poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) block copolymer.

[0022] Examples include PF series (CLARIANT), Series (BASF), PE series (CRODA), or Series (STEPAN).

[0023] When the polyoxyalkylene copolymer (b) is an EO-PO-EO block copolymer, the polyoxyalkylene copolymer (b) may contain up to 50% by weight of poly(ethylene oxide) blocks, preferably up to 40% by weight of poly(ethylene oxide) blocks, and more preferably up to 30% by weight of poly(ethylene oxide) blocks, relative to the total weight of the polyoxyalkylene copolymer (b). In this case, the polyoxyalkylene copolymer (b) may preferably contain more than 10% by weight of poly(ethylene oxide) blocks, relative to the total weight of the polyoxyalkylene copolymer (b). In the present invention, the poly(ethylene oxide) block is also known as a polyethylene glycol block.

[0024] The composition of the invention may comprise one or several dispersants (c), said dispersant(s) being more particularly different from the polyoxyalkylene copolymer (b).

[0025] The composition according to the invention may comprise from 0.1% to 20% by weight of dispersant and preferably from 1% to 10% by weight of dispersant relative to the total weight of the composition.

[0026] In a particular embodiment, the dispersant may be a polyoxyalkylene copolymer as previously defined, having an average molecular weight higher than 4000 g / mol, preferably 5000 g / mol, and more preferably 5600 to 6600 g / mol.

[0027] The polyoxyalkylene copolymer used as the dispersant may more preferably be an ethylene oxide-propylene oxide-ethylene oxide block copolymer (EO-PO-EO block copolymer), or in other words a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer or a poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) block copolymer.

[0028] When the dispersant is an EO-PO-EO block copolymer, the dispersant may comprise at least 30% by weight of poly(ethylene oxide) blocks, and preferably at least 40% by weight of poly(ethylene oxide) blocks relative to the total weight of the block copolymer.

[0029] In the present invention, the aqueous composition may contain at least 10% by weight of water, preferably at least 20% by weight of water, preferably at least 30% by weight of water, and more preferably at least 40% by weight of water relative to the total weight of the composition.

[0030] The composition of the present invention may further comprise one or more formulation additives well known in the art. In particular, the formulation additives may be selected from defoamers, wetting agents, antifreeze agents, antibacterial agents (or biocides), viscosity modifiers, and any mixtures thereof.

[0031] Each of the above-mentioned formulation additives can be added to the composition to obtain desired properties. For example, each of the formulation additives can be added to the composition in an amount of 0.0001% to 10% by weight, and preferably 0.001% to 5% by weight, relative to the total weight of the composition.

[0032] Other suitable formulation additives include, inter alia, antioxidants, colorants, flavors, adjuvants, attractants, binders, buffers, solid supports (carriers), coating agents, deodorants, emetics, inorganic fillers, safeners, pH adjusters, and any mixtures thereof known to those skilled in the art.

[0033] The composition of the present invention may further comprise an additional agrochemical. The additional agrochemical may be an insecticide, another fungicide, a herbicide, a synergist, a plant growth regulator, a nematicide, a plant nutrient, a plant fertilizer, and any mixture thereof.

[0034] The composition of the present invention may contain one or more of the above-mentioned one or more components in appropriate amounts to obtain corresponding properties as appropriate.

[0035] According to the invention, the composition can advantageously be used as a suspension concentrate (SC) or a suspoemulsion (SE).

[0036] In particular embodiments, the compositions of the present invention may involve:

[0037] - concentrates, which are designed to be added to farmers' water spray tanks, or

[0038] -Suspensions, which are produced in farmers' water spray tanks when the concentrate is mixed with water in the spray tank.

[0039] Another object of the present invention relates to a method for controlling or preventing infestation of plants by fungal organisms, which method comprises the foliar application of a composition according to the invention.

[0040] In this foliar method, the compositions of the invention may generally be applied as a spray composition, for example dispensed from a spray container.

[0041] The foliar method may involve applying an effective amount of the composition at a rate of 0.01 to 5 liters per hectare (L / ha), preferably 0.02 to 3.0 L / ha, and more preferably 0.1 to 2.0 L / ha.

[0042] Another object of the present invention relates to the use of the composition for controlling or preventing infestation of plants by fungal organisms.

[0043] In the present invention, the composition can be used to treat oilseed rape, especially against sclerotinia, alternaria and / or botrytis.

[0044] The following non-limiting examples demonstrate the improved behavior associated with the compositions according to the invention.

[0045] The components used in the following examples are detailed below:

[0046] - Fludioxonil is a fungicide (CAS No.: 131341-86-1); -Pluronic TM PE 6200 is a polyoxyalkylene copolymer (b) (CAS No.: 9003-11-6) having an average molecular weight of 2450 g / mol, supplied by BASF; and -Pluronic TM PE 6400 is a polyoxyalkylene copolymer (b) (CAS No.: 9003-11-6) with an average molecular weight of 2900 g / mol, supplied by BASF; - Polyox WSR N10 is a poly(ethylene oxide) (homopolymer) (CAS No.: 25322-68-3) with an average molecular weight of 100.000 g / mol, supplied by DuPont - Geropon DOS PG is sodium dioctyl sulfosuccinate (CAS No. 577-11-7), supplied by Solvay; -Pluronic TM PE 10400 is a dispersant (c) of a polyoxyalkylene copolymer (CAS No.: 9003-11-6) having an average molecular weight of 5900 g / mol, supplied by BASF; and -Morwet D-425 is a dispersant for naphthalenesulfonic acid sodium salt (CAS No. 68425-94-5), supplied by Nouryon.

[0047] The antifreeze agents, viscosity modifiers, biocides, antifoaming agents and wetting agents used in Examples 1 to 6 are components well known in the art for preparing suspension concentrates. Examples 1 and 2

[0048] Examples 1 and 2 provide compositions according to the invention which are suspension concentrates (SC).

[0049] Add the biocide and wetting agent to 70% by weight of water under stirring. TM PE10400 (preheated to 50°C for easier handling) was added to the mixture. After stirring for 10 min, the defoamer and antifreeze were added. While continuing to stir, Pluronic TM PE 6200 or Pluronic TM PE 6400 (preheated to 50°C for easier handling) was added to the mixture. Fludioxonil was added to the mixture and it was stirred for 20 min. The resulting mixture was milled using a dedicated Dyno mill KDL with 1 mm glass beads until d 50 <2.0μm and d 90 <8.0 μm. Particle size distribution was measured using a Malvern Mastersizer 3000. After the particle size distribution was achieved, a 2% mixture of the previously prepared viscosity modifier in water and the remaining water were added under stirring.

[0050] The concentrations of components added to form the compositions of Examples 1 and 2 are listed in Table 1 below and are expressed as percentage by weight (% w / w) relative to the total weight of the composition.

[0051] Table 1 Example 3-6

[0052] Examples 1 and 2 and Comparative Examples 3-6 are collected in Table 2. Comparative Examples 3-6 are also suspension concentrates (SC) and are prepared identically to Examples 1 and 2, except that the polyoxyalkylene copolymer (b) of the invention is replaced by Polyox WSR N10 (without preheating) or Geropon DOS PG (preheated at 50°C for easier handling), and the dispersant (c) of the invention is replaced by Morwet D-425 (without preheating).

[0053] The antifreeze agent, viscosity modifier, biocide, defoamer and wetting agent used in Table 2 were the same between all Examples 1 to 6, respectively.

[0054] Table 2

[0055] In order to evaluate the retention properties of the samples (Examples 1 to 6), the dynamic surface tension (DST) of the samples was measured using a Krüss bubble pressure tensiometer BP 100. The different samples were measured at a concentration of 0.33% in water. Samples showing a surface tension of 55 mN / m or less at a surface aging of 75 ms were considered to have good retention properties, while samples showing a surface tension of more than 55 mN / m at a surface aging of 75 ms were considered to have poor retention properties.

[0056] DST will be shown 75ms Example 1 is 53mN / m and shows DST 75ms Example 2 with 54 mN / m was evaluated as a sample with good retention properties. Formulations with improved retention properties show favorable behavior during foliar application because the composition droplets adhere better to the plant leaves.

[0057] To evaluate the stability of the samples (Examples 1 to 6), the viscosity of the samples, as well as the serum formation and the sediment formation were measured. These measurements were initially carried out after preparation of the formulation and after 2 weeks of storage at elevated temperature. Storage was carried out at 54°C and in a climate chamber with a cycling temperature between -10°C and 50°C.

[0058] The viscosity is measured using a Brookfield viscometer, using spindle S3 at 30 rpm. The viscosity is considered good when the initial viscosity is below 1000 mPa and the deviation from the initial viscosity during storage as described above does not exceed 10%.

[0059] The serum formation was measured using a ruler. The serum formation was considered good when it was less than 5% of the total formulation measurement.

[0060] The formation of sediment was evaluated by slow decanting followed by visual assessment. Any sediment formation was not tolerated. The result was considered good when no sediment formation was seen.

[0061] All results of DST and stability are collected in Table 3.

[0062] Table 3

[0063] Example 1 according to the invention has an initial viscosity of 675 mPa and has a deviation of less than 2% after storage, and Example 2 according to the invention has an initial viscosity of 588 mPa and has a deviation of less than 5% after storage. In Examples 1 and 2, less than 5% of the clear liquid formation (of the total formulation measured value) was observed and no formation of any sediment was observed. The low and constant viscosity proves excellent stability and results in formulations that are easy to handle even after long storage times (e.g. after 2 weeks of storage at high temperature). Comparative Examples 3-6 do not meet the required conditions in terms of DST and / or stability.

Claims

1. An aqueous composition comprising: (a) at least 10% by weight of fludioxonil relative to the total weight of the composition, (b) at least one polyoxyalkylene copolymer having an average molecular weight of up to 4000 g / mol, (c) at least one dispersant which is a polyoxyalkylene copolymer having an average molecular weight higher than 4000 g / mol, and (d) Water.

2. The composition according to claim 1, characterized in that The composition comprises 20% to 60% by weight of fludioxonil and preferably 30% to 50% by weight of fludioxonil relative to the total weight of the composition.

3. A composition according to any one of the preceding claims, characterized in that The polyoxyalkylene copolymer (b) has an average molecular weight of up to 3000 g / mol.

4. A composition according to any one of the preceding claims, characterized in that The composition comprises from 1 to 30% by weight of the polyoxyalkylene copolymer (b), and preferably from 1 to 20% by weight of the polyoxyalkylene copolymer (b), relative to the total weight of the composition.

5. A composition according to any one of the preceding claims, characterized in that The polyoxyalkylene copolymer (b) is a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer.

6. A composition according to any one of the preceding claims, characterized in that The composition comprises from 0.1% to 20% by weight of a dispersant relative to the total weight of the composition.

7. A composition according to any one of the preceding claims, characterized in that The dispersant (c) is a polyoxyalkylene copolymer having an average molecular weight of 5000 g / mol.

8. A composition according to any one of the preceding claims, characterized in that The dispersant (c) is a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer.

9. A composition according to any one of the preceding claims, characterized in that The composition is a suspension concentrate (SC) or a suspoemulsion (SE).

10. A method of controlling or preventing infestation of plants by fungal organisms, the method comprising foliar application of a composition according to any one of the preceding claims.

11. The method according to claim 10, characterized in that The plant is rapeseed.

12. Use of a composition according to any one of claims 1 to 9 for controlling or preventing infestation of plants by fungal organisms.

Images