WO2024115334A1

WO2024115334A1 - Formulation comprising fludioxonil

Info

Publication number: WO2024115334A1
Application number: PCT/EP2023/083069
Authority: WO
Inventors: Raphael Kleber; Aikaterini TSOUTSOURA
Original assignee: Syngenta Crop Protection Ag
Priority date: 2022-11-30
Filing date: 2023-11-24
Publication date: 2024-06-06
Also published as: AR131184A1

Abstract

This invention relates to a composition comprising: (a) at least 40% by weight of fludioxonil over the total weight of the composition, (b) lignosulfonate, and (c) optionally at least one polyoxyalkylene copolymer.

Description

FORMULATION COMPRISING FLUDIOXONIL

This invention relates to a composition comprising fludioxonil. More particularly, this invention relates to formulations such as water dispersible granules; to dilutions or dispersions of such formulations more particularly in a farmer’s spray-tank; and to use of such a composition in agriculture or horticulture for controlling, limiting or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Fludioxonil is a fungicidal agrochemical commercially available under different types of formulation. When a high loading of fludioxonil is needed, there is not a lot of solution on the market.

The aim of the present invention is to overcome the problems of the prior art techniques by proposing a composition comprising a high loading of fludioxonil, especially as solid formulation, which provides stability over time while guaranteeing satisfying sprayable conditions.

To this end, an object of the present invention is to provide a composition comprising:

(a) at least 40% by weight of fludioxonil over the total weight of the composition,

(b) lignosulfonate, and

(c) optionally at least one polyoxyalkylene copolymer.

Thanks to the composition of the present invention, all the above problems have been overcome. More particularly, the present invention provides a composition, more particularly a solid composition, with a optimized stability over time, while guaranteeing satisfying homogeneity and sprayable conditions. Furthermore, thanks to a high loading of fludioxonil, a lower amount of composition is needed per Hectare.

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

Hence, the composition of the present invention is more particularly a fungicidal composition.

The present invention can have a high amount of active ingredient, especially a high amount of fludioxonil such as at least 40% by weight over the total weight of the composition. More particularly, the composition can comprise from 40% to 90% by weight of fludioxonil, preferably from 40% to 80% by weight of fludioxonil, preferably from 60% to 80% by weight of fludioxonil, and more preferably more than 60% to 80% by weight of fludioxonil, over the total weight of the composition.

The composition according to the invention can comprise from 1 to 50 % by weight of lignosulfonate, preferably from 10 to 50 % by weight of lignosulfonate, preferably from more than 15% to 40% by weight of lignosulfonate, preferably from 20 to 40 % by weight of lignosulfonate, and preferably from 20 to 30 % by weight of lignosulfonate, over the total weight of the composition.

The composition according to the invention can comprise from 0 to 20% by weight of polyoxyalkylene copolymer, preferably from 0.1 to 20% by weight of polyoxyalkylene copolymer, and more preferably from 1 to 10% by weight of polyoxyalkylene copolymer, over the total weight of the composition.

In a preferred embodiment according to the present invention, the composition can comprise:

(a) from 40% to 90% by weight of fludioxonil over the total weight of the composition,

(b) from 1% to 30% by weight lignosulfonate, over the total weight of the composition, and

(c) from 0% to 10% by weight of at least one polyoxyalkylene copolymer, and preferably from 1% to 10% by weight of at least one polyoxyalkylene copolymer, over the total weight of the composition.

In another preferred embodiment according to the present invention, the composition can comprise:

(b) from 20% to 40% by weight lignosulfonate, over the total weight of the composition, and

(c) from 0% to 10% by weight of at least one polyoxyalkylene copolymer, and preferably from 1% to 10% by weight of at least one polyoxyalkylene copolymer over the total weight of the composition.

In the present invention, the lignosulfonate is more particularly a water-soluble anionic polymer which can be formed as by-product in the sulphite pulping process. Lignosulfonates have an average molecular weight typically in the range of about 500 to about 150000 g/mol. Lignosulfonates may comprise different metal or ammonium ions as counter cations of the sulfonate groups, such as for example copper, zinc, calcium, sodium, potassium, magnesium, or aluminum.

In a particular embodiment, the lignosulfonate can have an average molecular weight distribution in the range of about 1000 to about 100000 g/mol, preferably in the range of about 10000 to about 80000 g/mol, and more preferably in the range of about 20000 to about 60000 g/mol.

The term lignosulfonate can be defined as including lignosulfonate, lignosulfonic acid, lignosulfuric acid, lignin sulfonate, ligninsulfonic acid, or other expressions well-known in the art.

More preferably, the lignosulfonate can be a salt of lignosulfonic acid, such as sodium lignosulfonate and/or calcium lignosulfonate.

The composition can comprise one or several polyoxyalkylene copolymers, more particularly having an average molecular weight from 1000 to 8000 g/mol, preferably from 2000 to 8000 g/mol, preferably from 4000 to 7000 g/mol, and more preferably from 5000 to 6000 g/mol.

In the present invention, the expression “an average molecular weight of” means “a molecular weight which is approximately of”. Molecular weight of a polymer, or in other words the molar mass, can be easily determined by method well-known in the art, such as gel permeation chromatography (GPC).

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

The polyoxyalkylene copolymer can be more preferably a polyoxyalkylene block copolymer of the AB, ABA, BAB, or ABABA type.

More particularly, the polyoxyalkylene copolymer can be prepared by ring-opening polymerization of the corresponding cyclic ethylene oxide and propylene oxide monomers.

Typically, the ring-opening polymerization is initiated by addition of water and alkali 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, before adding a second monomer to form further polymer blocks.

In a preferred embodiment, the polyoxyalkylene copolymer can be a poly(ethylene oxide)-poly(propylene oxide) copolymer, and more particularly a poly(ethylene oxide)-poly(propylene oxide) block copolymer, and even more particularly a butyl based polyalkylene oxide block copolymer.

Examples include the GENAPOL^® PF series (CLARIANT), the PLURONIC^® series (BASF), the SYNPERONIC^® PE series (CRODA), or the TOXIMUL^® series (STEPAN).

In a particular embodiment according to the present invention, the composition comprises less than 9.8 % by weight, preferably up to 8 % by weight, preferably up to 5 % by weight, preferably up to 2 % by weight, and more preferably 0 % by weight, of a naphthalene sulfonic acid, over the total weight of the composition. For example, the naphthalene sulfonic acid can be a naphthalene sulfonic acid, sodium salt condensed with formaldehyde.

The composition of the invention can further comprise one or more formulation additives well-known in the art. In particular, the formulation additives can be selected among an anti-foam agent, a wetting agent, an anti-freeze agent, an anti-bacterial agent (or biocide), a viscosity modifier, and any mixture thereof.

Each of the above-cited formulation additives can be added into the composition to obtain the desired property. For example, each of the formulation additives can be added into the composition in an amount from 0.0001% to 10% by weight, and preferably from 0.001% to 5% by weight, over the total weight of the composition.

In a preferred embodiment, the composition according to the present invention can further comprise an antifoam agent, more particularly in an amount from 0.01% to 2% by weight over the total weight of the composition.

Other suitable formulation additives include amongst others known to the person skilled in the art, antioxidant, colourant, perfume, adjuvant, attractant, binder, buffer, solid support (carrier or filler), coating agent, deodorant, emetic agent, inorganic filler, safener, pH modifier, and any mixture thereof. The solid support can be more particularly an inert support (e.g. inert carrier or inert filler) such as inert organic or inorganic support well-known in the art. For example, the solid support can be calcium carbonate, talc, celite or lactose (lactose hydrate).

Each of the above-cited other formulation additives can be added into the composition to obtain the desired property. For example, each of the other formulation additives can be added into the composition in an amount from 0.0001% to 40% by weight, and preferably from 0.001% to 30% by weight, over the total weight of the composition.

In a preferred embodiment, the composition according to the present invention can further comprise a solid support (carrier or filler), more particularly in an amount from 1% to 40% by weight, and preferably in an amount from 10% to 30% by weight, over the total weight of the composition.

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

The composition of the present invention may comprise a suitable amount of one or several of the above-mentioned ingredient(s) to obtain the respective properties, when appropriate.

According to the present invention, the composition can be advantageously used as granules, and more particularly as water dispersible granules.

In a particular embodiment, the composition of the present invention may relate to:

- a concentrate (such as for examples granules) designed to be added to a farmer’s spray tank of water, or

- a suspension produced in a farmer’s spray tank of water when a concentrate (such as for example granules) is mixed with water in the spray tank.

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

In this foliar method, the composition of the present invention can be generally applied in spraying the composition, for example dispensed from a spray container.

Said foliar method can involve an effective amount of the composition applied at a rate of from 0.01 to 5 kilogram per Hectare (kg/ha), preferably from 0.1 to 3.0 kg/ha, and more preferably from 0.2 to 1.0 kg/ha. A preferred application rate can be from 0.2 to 0.7 kg/ha.

The effective amount can be expressed in gram of active ingredient (fludioxonil) per Hectare (gAI/ha). In this respect, said foliar method can involve an effective amount of the composition applied at a rate of from 10 to 500 gAI/ha, preferably from 50 to 400 gAI/ha, preferably from 100 to 300 gAI/ha, and more preferably from 200 to 250 gAI/ha.

Another object of the present invention relates to a use of the composition to control, limit or prevent an infestation of plants by fungal organisms.

In the present invention, the composition can be used to treat plants against sclerotinia, alternaria and/or botrytis .

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.

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.

Another object of the present invention relates to a process for the preparation of a composition as defined in the present invention, the obtained composition being preferably granules, and more preferably water dispersible granules, characterized in that it comprises the following steps:

i. preparing a solution comprising (a) fludioxonil, (b) lignosulfonate, (c) optionally at least one polyoxyalkylene copolymer, and (d) water;

ii. spray-drying agglomerating the solution of step i, to obtain said composition.

In a particular embodiment, the solution of step i can comprise:

- from 10% to 60% by weight of fludioxonil, and preferably 20% to 50% by weight of fludioxonil,

- from 1% to 30% by weight of lignosulfonate, and preferably 10% to 20% by weight of lignosulfonate,

- from 0% to 10% by weight of polyoxyalkylene copolymer, and preferably 1% to 5% by weight of polyoxyalkylene copolymer, and

- from 30% to 60% by weight of water, and preferably from 40% to 55% by weight of water,

over the total weight of the solution.

In step i, the solution is more particularly a liquid solution in the form of a suspension concentrate. Said solution can be prepared as follows: a mixture of (a) fludioxonil, (b) lignosulfonate, (c) optionally at least one polyoxyalkylene copolymer, and (d) water is prepared under stirring. More particularly, an additional mixing with a high-shear mixer can be used, especially to limit or remove lumps. Then the mixture is milled, in using a conventional milling device.

In step ii, the composition is more particularly a solid composition, especially under the form of granules, and more particularly of water dispersible granules. Said composition can be prepared by using a spray drying and agglomeration granulator well-known in the art. More particularly, the spray-drying agglomeration step can comprise an atomisation of the solution of step i.

The following non-limiting examples demonstrate the improved behaviour associated with a composition according to the present invention.

The components used in the following examples are detailed as follows:

Fludioxonil is a fungicide (CAS number: 131341-86-1);
Dispersing Agent 1 is the product commercialized by Borregaard AS under the name Ufoxane 3A, comprising more than 90% by weight of sodium lignosulfonate (lignosulfonic acid, sodium salt);
Dispersing Agent 2 is a naphthalene sulfonic acid, sodium salt condensed with formaldehyde, commercialized by Indorama Ventures, under the name Tersperse 2020;
Dispersing agent 3 is a copolymer of ethylene oxide and propylene oxide, with an average molecular weight of 5500 g/mol, commercialized by Stepan S under the name Toximul 8320;
Dispersing agent 4 is a copolymer of ethylene oxide and propylene oxide, with an average molecular weight of 2500 g/mol, commercialized by Croda under the name Synperonic PE/L62;
Anti-foam agent is polydimethylsiloxane commercialized by Elkem Silicones under the name Rhodorsil AF-454;
Carrier 1 is calcium carbonate commercialized from Omya; and
Carrier 2 is lactose, commercialized by DFE Pharma under the name Pharmatose 200M.

In a first step, a suspension concentrate, more particularly a slurry, is prepared in using the components gathered in table 1.

Table 1 gathers the concentrations of the components added to form said liquid solution of Examples 1 to 5, said concentrations being expressed in percentage by weight over the total weight of the composition (% w/w).

Examples	1	2	3	4	5
Fludioxonil	25	38.5	38.5	38.5	38.5
Dispersing agent 1	12.5	8.25	13.475	2.75	0
Dispersing agent 2	0	5.39	0	0	2.75
Dispersing agent 3	0	2.75	2.75	1.375	1.375
Dispersing agent 4	2.5	0	0	0	0
Antifoam agent	0.25	0.11	0.275	0.275	0.275
Carrier 1	0	0	0	12.1	12.1
Carrier 2	9.75	0	0	0	0
Water	50	45	45	45	45

Table 1

The liquid solution is prepared as follows: under stirring a first dispersing agent is added to water (dispersing agent 1 for examples 1-4, and dispersing agent 2 for example 5). Other dispersing agent(s) is/are added to the mixture, and finally the anti-foam agent, and optionally the carrier, is/are added to the mixture. After 10 min of stirring, Fludioxonil is added to the mixture and homogenized. With a high-shear mixer, lumps are suppressed and grinded. The resulting mixture is then milled, using a Dyno mill KDL-special with 1 mm glass beads until a d₅₀ < 2.5 µm and a d₉₀ < 8.0µm could be reached. The particle size distribution is measured, using a Cilas 920 equipment. The obtained liquid solution is a suspension concentrate, and more particularly a slurry.

In a second step, a solid composition, more particularly water dispersible granules, is prepared from the slurry obtained in the first step.

Table 2 gathers the concentrations of the components to form the solid composition of Examples 1 to 5, said concentrations being expressed in percentage by weight over the total weight of the composition (% w/w).

Examples	1	2	3	4	5
Fludioxonil	50	70	70	70	70
Dispersing agent 1	25	15	24.5	5	0
Dispersing agent 2	0	9.8	0	0	5
Dispersing agent 3	0	5	5	2.5	2.5
Dispersing agent 4	2.5	0	0	0	0
Antifoam agent	0.5	0.2	0.5	0.5	0.5
Carrier 1	0	0	0	22	22
Carrier 2	19.5	0	0	0	0

Table 2

The solid composition is prepared as follows: by using a spray drying and agglomeration granulator with an inlet temperature of the process air in the range of 80-100°C, the liquid solution of Table 1 is atomised trough a 1.8mm nozzle at 2 bar pressure to generate fine droplets. The water is evaporated, and dust is generated. By continuously spraying, granules start to form by agglomeration, more particularly in the form of raspberry structure. Granules with particle size below 0.2 mm are reinjected in the granulator to be further agglomerated. The obtained granule size ranges from 0.2 to 1.6 mm. Advantageously, said obtained granules are close to an absolute dust free product.

The results on wet sieve residue, suspensibility as well as persistent foam are gathered in table 3.

To evaluate the wet sieve residue according to the SQA 15.1 method based on CIPAC MT185, 50g of product are poured into 500mL of water. After 1 minute of standing, it is stirred for 5 minutes. The resulting suspension is then poured over a 45 µm fine mesh sieve. The sieve can be rinsed for up to 10 minutes with tap water. The residue on the sieve is collected, dried and weighed. The result is presented as a percentage over the initial 50g. After storage for 2 weeks at 54°C, the test is performed again representing a shelf-life of 2 years at 20°C. The wet sieve residue evaluation is satisfied when the initial residue as well as the residue after storage are below 0.20%, and preferably below 0.10%.

To evaluate the suspensibility according to the SQA 16.2 method based on CIPAC MT184, 2.5g of product are weighed into a 30°C preheated cylinder with 250mL of water SHW “D” (Standard Water Hardness of D 342 ppm and pH 6-7). The cylinder is inverted 180°, 30 times to disperse the product (each inversion taking approximatively 2 seconds). Afterwards, the cylinder is put into a 30°C water bath and left standing for 30 minutes. Once the time is up, 90% in volume of the 250mL solution is sucked out from the top and the rest is transferred into a glass beaker to be dried and weighed. The dried residue (solid) is used to calculate the suspensibility of the product. After storage for 2 weeks at 54°C, the test is performed again representing a shelf-life of 2 years at 20°C. The suspensibility evaluation is satisfied when the initial suspensibility as well as the suspensibility after storage are at least of 80%, and preferably of at least 90%.

To evaluate the persistent foaming according to the SQA 19.2 method based on CIPAC MT47.3, 180ml of water SHW “D” (Standard Water Hardness of D 342 ppm and pH 6-7) is put into a 250ml measuring cylinder and the required amount of product is added into the cylinder. The amount of product requires to make 200ml of a dispersion at the highest recommended application concentration. After adding the product, the cylinder is topped up with water SHW “D” to 200ml mark. A stopper is put on the cylinder and the cylinder is inverted 30 times, each inversion taking approximately 2 seconds. Afterwards, the cylinder is stood undisturbed and the volume of foam (expressed in ml) remaining after 1 min is read. A few bubbles around the periphery are not significant. The persistent foaming evaluation is satisfied when the volume of foam is less than 20 ml, and preferably less than 10 ml.

Examples		1	2	3	4	5
Wet sieve residue (%)	initial	0	0	0	0	0.15
Suspensibility (%)	initial	97	92	96	92	90
Persistent foaming (ml)	initial	0	50	8	2	2
Wet sieve residue (%)	after storage	0.05	0.256	0	0.164	0.352
Suspensibility (%)	after storage	97	90	96	80	67

Table 3

Claims

A composition comprising:
(a) at least 40% by weight of fludioxonil over the total weight of the composition,
(b) lignosulfonate, and
(c) optionally at least one polyoxyalkylene copolymer.
A composition according to claim 1, characterized in that the composition comprises up to 90% by weight of fludioxonil over the total weight of the composition.
A composition according to claim 1 or 2, characterized in that the composition comprises from 40% to 80% by weight of fludioxonil, preferably from 60% to 80% by weight of fludioxonil, over the total weight of the composition.
A composition according to any one of the preceding claims, characterized in that the composition comprises from 1% to 50% by weight of lignosulfonate, preferably 10% to 50% by weight of lignosulfonate, and more preferably from 20% to 40% by weight of lignosulfonate, over the total weight of the composition.
A composition according to any one of the preceding claims, characterized in that the composition comprises from 0.1% to 20% by weight of polyoxyalkylene copolymer, and preferably from 1% to 10% by weight of polyoxyalkylene copolymer, over the total weight of the composition.
A composition comprising:
from 40% to 90% by weight of fludioxonil over the total weight of the composition,

from 1% to 30% by weight lignosulfonate, over the total weight of the composition, and

from 0% to 10% by weight of at least one polyoxyalkylene copolymer, and preferably from 1 to 10% by weight of at least one polyoxyalkylene copolymer, over the total weight of the composition.
A composition comprising:
from 40% to 90% by weight of fludioxonil over the total weight of the composition,

from 20% to 40% by weight lignosulfonate, over the total weight of the composition, and

from 0% to 10% by weight of at least one polyoxyalkylene copolymer, and preferably from 1% to 10% by weight of at least one polyoxyalkylene copolymer, over the total weight of the composition.
A composition according to any one of the preceding claims, characterized in that the lignosulfonate is a sodium salt of lignosulfonic acid.
A composition according to any one of the preceding claims, characterized in that the polyoxyalkylene copolymer is a poly(ethylene oxide)-poly(propylene oxide) copolymer.
A composition according to any one of the preceding claims, characterized in that it further comprises an antifoam agent.
A composition according to any one of the preceding claims, characterized in that the composition is granules, and preferably water dispersible granules.
A method of controlling, limiting or preventing an infestation of plants by fungal organisms, which comprises the foliar application of the composition according to any one of the preceding claims.
A method according to claim 12, characterized in it is used to treat plants against sclerotinia, alternaria and/or botrytis.
Use of a composition according of any one of claims 1 to 11 to control, limit or prevent an infestation of plants by fungal organisms.
Process for the preparation of a composition according to any one of claims 1 to 11, characterized in that it comprises the following steps:
preparing a solution, more preferably a suspension concentrate, comprising (a) fludioxonil, (b) lignosulfonate, (c) optionally at least one polyoxyalkylene copolymer, and (d) water; and
spray-drying agglomerating the solution of step i., to obtain said composition.
Process according to claim 15, characterized in that the solution of step i comprises from 10% to 60% by weight of fludioxonil, from 1% to 30% by weight of lignosulfonate, from 0% to 10% by weight of polyoxyalkylene copolymer, and from 30 % to 60% by weight of water, over the total weight of the solution.