Emulsifiable concentrates containing allyl isothiocyanate and their use as nematicides in crop plants - Patents.com

Abstract

The present invention relates to an agrochemical emulsifiable concentrate comprising: allyl isothiocyanate; at least one vegetable oil; at least one nonionic surfactant; and at least one anionic surfactant. The present invention also relates to the use of said emulsifiable concentrate as a nematicide in crop plants.

Description

[Technical field]

[0001] The present invention relates to emulsifiable concentrates containing allyl isothiocyanate and their use as nematicides in crop plants. [Background technology]

[0002] Disinfection or disinfection of agricultural soils is a practice which makes it possible to cleanse the soil of both animal and plant parasites which live in the soil and cause damage to agricultural crops. There are various physical or chemical systems to accomplish this, including exposure to sunlight, injection of steam into the soil, or treatment with chemicals that have a fumigation effect, also called fumigants, which exert an anti-parasitic effect when properly distributed on or incorporated into the soil.

[0003] Fumigants are products that have the property that they are capable of existing in a gaseous state at certain specific conditions of temperature and pressure, in sufficient concentrations and for sufficient time to permit the elimination of targeted parasites in the soil. However, because fumigants are generally volatile compounds that are irritating to the skin and eyes, are also corrosive and sometimes flammable, they must be decanted from sealed containers to holding tanks and their subsequent agricultural application must be carried out by professional users wearing appropriate personal protective equipment.

[0004] Among the various fumigants currently in use, mention may be made of allyl isothiocyanate (AITC), a naturally occurring compound present in mustard oil and known for its excellent fungicidal, bactericidal and nematicidal properties. This substance is conventionally applied by professional personnel in formulations with very high AITC concentrations, for example more than 70% by weight, in order to effectively control plant pathogens present in the soil.

[0005] However, despite the great effectiveness of this technology, fumigation is currently a complex process to manage and involves high costs. Summary of the Invention

[0006] In view of the above, the Applicant set himself the goal of identifying formulations which contain relatively low concentrations of allyl isothiocyanate, in particular lower concentrations of allyl isothiocyanate than formulations of the prior art, and which are therefore easier to use in the agricultural field, but at the same time exhibit high fumigation efficacy.

[0007] In particular, it is an object of the present invention to provide an effective formulation that can be used by all operators in the agricultural sector without having to rely on professional users who are properly trained in the use of fumigants. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The Applicant has now found that these and other problems, which will be better explained in the following description, can be at least partially solved by using an emulsifiable concentrate comprising allyl isothiocyanate dissolved in at least one vegetable oil. The use of vegetable oil as a solvent for allyl isothiocyanate makes it possible to obtain an emulsifiable concentrate which is surprisingly stable over time, with which it is possible to easily obtain a homogeneous and stable oil-in-water emulsion after dilution with water. The emulsifiable concentrate exhibits sufficient nematicidal activity, even though it contains a relatively low concentration of AITC as an agrochemically active ingredient.

[0009] The first object of the present invention is therefore Allyl isothiocyanate At least one type of vegetable oil At least one nonionic surfactant At least one anionic surfactant and an agrochemical emulsifiable concentrate comprising:

[0010] A second subject of the invention is the use of said agrochemical emulsifiable concentrates for controlling nematodes in crop plants.

[0011] Preferably, allyl isothiocyanate is present in the emulsifiable concentrate in an amount ranging from 1% to 70% by weight, more preferably from 5% to 45% by weight, and even more preferably from 15% to 25% by weight, based on the weight of the emulsifiable concentrate.

[0012] Preferably, the vegetable oil is selected from rapeseed oil, soybean oil, olive oil, castor oil, linseed oil, including derivatives esterified with C1-C6 alkyl groups.

[0013] Esterified derivatives of vegetable oils may be obtained by transesterification of vegetable oils with short chain alcohols (C1-C6), such as methanol, ethanol, butanol and pentanol, or by esterification of the fatty acids resulting from saponification of vegetable oils with the same alcohols.

[0014] Preferably, the vegetable oil is rapeseed oil, more preferably the vegetable oil is a C1-C6 ester of rapeseed oil, even more preferably the vegetable oil is a methyl ester of rapeseed oil.

[0015] The vegetable oil is present in an amount suitable to obtain a desired total volume of the emulsifiable concentrate. Generally, the vegetable oil is present in the emulsifiable concentrate in a total amount ranging from 1% to 90% by weight, preferably from 40% to 70% by weight, based on the weight of the emulsifiable concentrate.

[0016] As mentioned above, the Applicant has discovered that the use of vegetable oils as solvents for allyl isothiocyanate makes it possible to obtain emulsifiable concentrates comprising this agrochemically active ingredient which are surprisingly stable over time and have a high propensity to form homogeneous and stable emulsions after dilution with water.

[0017] As is well known to those skilled in the art, an agrochemical emulsifiable concentrate is a specific type of agrochemical liquid formulation in which an agrochemically active ingredient is dissolved in a solvent that is substantially immiscible in water in the presence of surfactants such as emulsifiers, wetting agents, defoamers, antifreeze agents, and biological activators that make the agrochemical liquid formulation more suitable for use in agriculture.

[0018] According to the present invention, the emulsifiable concentrate comprises at least one nonionic surfactant and one anionic surfactant.

[0019] The nonionic surfactant functions primarily as an emulsifier - that is, its presence in the emulsifiable concentrate promotes emulsification of the oil phase in the water used to dilute the emulsifiable concentrate, resulting in a homogeneous final, ready-to-use formulation.

[0020] Preferably, the at least one nonionic emulsifying surfactant is selected from ethoxylated block copolymers, etho-propoxylated block copolymers, ethoxylated tristyrylphenol, etho-propoxylated tristyrylphenols, ethoxylated tristyrylphenol phosphate (acid form), ethoxylated tristyrylphenol sulfate (acid form), sorbitan monolaurate, ethoxylated sorbitan monolaurate, sorbitan monooleate, ethoxylated sorbitan monooleate, ethoxylated vegetable oils, ethoxylated fatty alcohols, organosilicon compounds, and mixtures thereof. More preferably, the at least one nonionic surfactant is ethoxylated tristyrylphenol.

[0021] Preferably, the at least one nonionic surfactant emulsifier is present in the emulsifiable concentrate in a total amount ranging from 1% to 20% by weight, more preferably from 5% to 15% by weight, based on the weight of the emulsifiable concentrate.

[0022] Preferably, the at least one anionic surfactant is selected from ethoxylated tristyrylphenol phosphate (salified form), ethoxylated tristyrylphenol sulfate (salified form), calcium dodecylbenzene sulfonate, and mixtures thereof. More preferably, the at least one anionic surfactant is selected from calcium dodecylbenzene sulfonate and ethoxylated tristyrylphenol phosphate (salified form).

[0023] The at least one anionic surfactant is present in the emulsifiable concentrate in a total amount ranging from 1% to 20% by weight, more preferably from 1% to 10% by weight, based on the weight of the emulsifiable concentrate.

[0024] Optionally, the emulsifiable concentrate of the present invention may contain further co-ingredients other than those listed above, such as, for example, compounds for improving the biological activity of the emulsifiable concentrate, anti-drift agents, penetrating agents, wetting agents, antifoaming agents, stabilizing agents, sequestering agents, anticorrosive agents, tackifiers, etc.

[0025] In a preferred embodiment, the agrochemical emulsifiable concentrate according to the invention comprises (in % by weight based on the weight of the emulsifiable concentrate): 5% to 45% by weight, preferably 15% to 25% by weight, of allyl isothiocyanate 5% to 15% by weight of at least one nonionic surfactant 1% to 10% by weight of at least one anionic surfactant at least one vegetable oil in an amount equal to the remainder necessary to bring the weight of the emulsifiable concentrate to 100% by weight; Includes.

[0026] The emulsifiable concentrates of the present invention can be prepared by methods known to those skilled in the art by mixing the components in the desired ratio without any particular restriction on the order in which the components are mixed.

[0027] For example, in a first step, the active ingredient allyl isothiocyanate can be dissolved in a vegetable oil; in a second step, at least one nonionic surfactant and at least one anionic surfactant are added to the mixture obtained in the first step.

[0028] According to one alternative process, allyl isothiocyanate is added to a mixture including a vegetable oil, a nonionic surfactant, and an anionic surfactant.

[0029] The emulsifiable concentrate according to the invention exhibits a high level of nematicidal activity without exhibiting phytotoxicity towards the crop to which it is applied.

[0030] Moreover, although the emulsifiable concentrate of the present invention has a lower allyl isothiocyanate concentration than that commonly used in state-of-the-art fumigants, the biological effectiveness of the emulsifiable concentrate of the present invention is fully comparable to that of state-of-the-art fumigants. In addition, the emulsifiable concentrate of the present invention has the advantage of greater ease of application, since it can also be safely used by non-professional users for the treatment of crop plants.

[0031] Examples of nematodes which can be controlled with the agrochemical emulsifiable concentrates of the invention are Pratylenchus spp., Globodera spp., Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp., and the like. spp.), Belonolaimus spp., and others.

[0032] Examples of crop plants in which the agrochemical emulsifiable concentrates of the present invention can be used to control nematodes include fruit trees, coffee, cocoa, vegetables, turf, and a wide variety of crops such as rice, wheat, and soybeans.

[0033] Another object of the present invention is a method for controlling nematodes in crop plants, comprising applying to the crop plants at least one effective dose of the agrochemical emulsifiable concentrate of the present disclosure.

[0034] The emulsifiable concentrate according to the invention can be applied as such or in diluted form to any part of the plant, for example to the leaves, to the trunk, to the branches and to the roots, or to the seeds themselves before sowing, or to the soil in which the plants are to be grown.

[0035] The emulsifiable concentrates according to the invention are preferably applied to crop plants in a form diluted with water, forming an oil-in-water emulsion.

[0036] The emulsifiable concentrates of the present invention can be used to prepare oil-in-water emulsions by combining the concentrate with water, optionally in the presence of other ingredients such as wetting agents, emulsifiers, etc. These additional ingredients may also be present or they may be present only in the water used to dilute the emulsifiable concentrate.

[0037] Thus, a further object of the present invention is Providing at least one emulsifiable concentrate according to the present invention; diluting said emulsifiable concentrate with water to obtain an agricultural formulation in the form of an oil-in-water emulsion; A process for preparing an agricultural formulation in the form of an oil-in-water emulsion comprising:

[0038] Water is added in the amount necessary to achieve the required oil-in-water emulsion volume.

[0039] The amount of the emulsifiable concentrate or the relative emulsion applied to a crop plant to obtain a desired agrochemical effect may vary depending on various factors, such as the crop in question, climatic conditions, soil characteristics, application method, etc.

[0040] In order to better illustrate the present invention, the following example embodiments are given which should be understood as illustrative and not limiting. EXAMPLES

[0041] Example 1: Emulsifiable concentrate containing allyl isothiocyanate An emulsifiable concentrate IRF265-2 having the composition shown in Table 1 was prepared according to the present invention. The commercial products used to prepare the oil dispersions are: Amesolv CME, which is a mixture of methyl esters(plural) of rapeseed oil fatty acids(plural). • Soprophor 796 / P, which is an eth-propoxylated tristyrylphenol. • Rhodacal 60 / BE, which is the calcium salt of benzenesulfonic acid.

[0042] [Table 1]

[0043] The emulsifiable concentrate IRF265-2 was subjected to an accelerated stability test according to Cipac MT46.1, which aims to accelerate the ageing of the product by heating, making it possible to simulate the stability of the formulation after 2 years of storage at room temperature.

[0044] The following procedure was used: a quantity of the formulation (e.g., 500 mL) was placed in a closed container and placed in a heater at 54° C. for 14 days. After this, the container was removed from the heater and allowed to return to room temperature, thereby visually demonstrating that the formulation did not exhibit phase separation or other phenomena of physical instability, such as flocculation, aggregation, or crystal growth. The chemical stability of the active agrochemical ingredients is also demonstrated, as is the quality of the dispersion subjected to accelerated stability testing after dilution with water. The IRF265-2 sample remained homogeneous at the end of heat treatment and passed accelerated aging tests.

[0045] Example 2: Determination of nematicidal activity against plant parasitic nematodes The tests aimed at testing the nematicidal activity of the products under test were carried out in soils naturally infested with species of plant parasitic nematodes, either under protected cultivation conditions or in the open field. Prior to the start of the experiments, a qualitative-quantitative assessment of the presence of parasites was carried out by taking and analysing soil samples.

[0046] All the tested products were applied by fertigation, using a hose with a diameter of 16 mm and a distance of 10 cm between dispensing holes connected to a layflat that was spread on the ground along the entire length of the treatment area. The layflat was connected to a pump that drew water from the irrigation system and mixed the product directly into it by a Venturi system. Pressure gauges connected at the beginning and end of the layflat made it possible to check the water pressure inside the treatment system. The hose, spread perpendicular to the layflat, was covered with a plastic sheet suitable for applying fumigant products. Before treatment, the soil was properly irrigated to promote the distribution of the active ingredient in the soil.

[0047] The following products were tested: Emulsifiable concentrate IRF265-2 of Example 1 Dominus™, a commercial fumigant containing 96.3% AITC by weight • Vapam™, a commercial fumigant containing 38.8% Metam-sodium by weight. The tested products were applied to bare soil after dilution with water: IRF265-2 and Dominus™ 14 days before sowing or transplanting, Vapam™ according to its label.

[0048] Product performance evaluation is Detection of phytotoxic effects (using a scale of 0-10: 0 = no symptoms, 10 = destroyed plant), A determination of plant growth (measured on a scale of 1 to 5 or by the NDVI "Normalized Difference Vegetation Index"), and Effectiveness against nematodes (by analysing the number of J2 larvae present in the soil or by assessing the root-knot nematode infestation index in the root system using the Bridge & Page scale) It included:

[0049] The following tables show data collected from trials conducted on different crops and nematode species (1 US gallon / acre = 9.35 L / hectare). Table 2 shows the results of tests on onions infested with certain root-knot nematodes (Meloidogyne spp.).

[0050] [Table 2]

[0051] Table 3 shows the results of tests on potatoes infested with Columbia root-knot nematodes (Meloidogyne chitwoodi). [Table 3]

[0052] Table 4 shows the results of tests on potatoes infested with Pratylenchus coffeae. [Table 4]

[0053] Table 5 shows the results of tests on cucumbers infested with Meloidogyne incognita. [Table 5]

[0054] From the results obtained in the experiments carried out on different crops against different nematodes it can be concluded that when the formulation is applied at the same dose, the product IRF265-2 according to the invention shows an efficacy and selectivity that is fully comparable to the commercial product Dominus®, despite it containing only 20% of the agrochemical active ingredient allyl isothiocyanate.

[0055] Example 3: Stability Study The emulsifiable concentrate IRF265-2 was subjected to further stability tests (according to Cipac MT 36) to evaluate the stability of the oil-in-water emulsion of the product after 24 hours. For comparison, several emulsifiable concentrates containing solvents other than vegetable oils were also prepared (References 1 to 3) and subsequently subjected to the same stability tests. The composition of the emulsifiable concentrates prepared and tested is shown in Table 6.

[0056] [Table 6]

[0057] For the stability test, the emulsifiable concentrate formulations were poured into standard D Cipac water (hardness 342 ppm) at a concentration of 5% v / v according to test MT36. The following procedure was used: a 100 mL graduated glass cylinder was filled with 95 mL of standard Cipac D water, 5 mL of emulsifiable concentrate was added and the glass cylinder was sealed with a glass stopper. The cylinder was turned upside down 30 times, left at 30° C. and the stability of the emulsion formed was observed after 30 minutes, 2 hours and 24 hours. Observations regarding the stability of these emulsifiable concentrates after 30 minutes, 2 hours and 24 hours are reported in Table 7.

[0058] [Table 7]

[0059] The term "stable" means that no oil separation or heterogeneity is detectable in the emulsion. The word ".d." stands for undecided. As can be seen from Table 7, the emulsifiable concentrate IRF265-2 according to the invention had a was also stable, whereas the control was already unstable after 2 hours. [1] Allyl isothiocyanate At least one type of vegetable oil At least one nonionic surfactant At least one anionic surfactant An agrochemical emulsifiable concentrate comprising: [2] The agrochemical emulsifiable concentrate according to [1], wherein the at least one vegetable oil is selected from rapeseed oil, soybean oil, olive oil, castor oil, linseed oil, including derivatives esterified with C1-C6 alkyl groups. [3] The agrochemical emulsifiable concentrate according to [1], wherein the vegetable oil is rapeseed oil, preferably a C1-C6 ester of rapeseed oil. [4] The agrochemical emulsifiable concentrate according to one or more of [1]-[3], wherein the allyl isothiocyanate is present in an amount ranging from 1% to 70% by weight, preferably from 5% to 45% by weight, more preferably from 15% to 25% by weight, based on the weight of the emulsifiable concentrate. [5] The agrochemical emulsifiable concentrate according to one or more of [1]-[4], wherein the at least one vegetable oil is present in an amount ranging from 1% to 90% by weight, preferably from 40% to 70% by weight, based on the weight of the emulsifiable concentrate. [6] The at least one nonionic surfactant may be selected from the group consisting of ethoxylated block copolymers, eth-propoxylated block copolymers, ethoxylated tristyrylphenol, eth-propoxylated tristyrylphenol, ethoxylated tristyrylphenol phosphate (acid form), ethoxylated tristyrylphenol sulfate (acid form), sorbitan monolaurate, ethoxylated sorbitan monolaurate, sorbitan monooleate, ethoxylated sorbitan monooleate, ethoxylated vegetable oils, ethoxylated fatty alcohols, organosilicon compounds, and mixtures thereof. The agrochemical emulsifiable concentrate according to any one or more of the above [1]-[5], selected from the group consisting of: [7] The agrochemical emulsifiable concentrate according to one or more of [1]-[6], wherein the at least one surfactant is present in the emulsifiable concentrate in an amount ranging from 1% to 20% by weight, preferably from 5% to 15% by weight, based on the weight of the emulsifiable concentrate. [8] The at least one anionic surfactant may be ethoxylated tristyrylphenol phosphate (salt form), ethoxylated tristyrylphenol salt sulfate (salified form), calcium dodecylbenzenesulfonate, 10. The agrochemical emulsifiable concentrate according to any one or more of the preceding claims [1]-[7], which is selected from the group consisting of ethylhexyl ether, ... [9] The agrochemical emulsifiable concentrate according to one or more of the above [1]-[8], wherein the at least one anionic surfactant is present in the emulsifiable concentrate in an amount ranging from 1% to 20% by weight, preferably from 1% to 10% by weight, based on the weight of the emulsifiable concentrate.

[10] (as weight percent based on weight of emulsifiable concentrate) 5% to 45% by weight, preferably 15% to 25% by weight, of allyl isothiocyanate 5% to 15% by weight of at least one nonionic surfactant 1% to 10% by weight of at least one anionic surfactant at least one vegetable oil in an amount equal to the remainder necessary to bring the weight of the emulsifiable concentrate to 100% by weight; The agrochemical emulsifiable concentrate according to [1] above.

[11] Providing at least one agrochemical emulsifiable concentrate according to [1] above; diluting said emulsifiable concentrate with water to obtain an agricultural formulation in the form of an oil-in-water emulsion; 1. A process for preparing an agricultural formulation in the form of an oil-in-water emulsion, comprising:

[12] applying at least one effective dose of the agrochemical emulsifiable concentrate according to [1] to a crop plant; The concentrate is applied in undiluted form or diluted with water to form an oil-in-water emulsion; A method for controlling nematodes in crop plants.

[13] Use of the agrochemical emulsifiable concentrate according to [1] as a nematicide in crop plants, comprising: The concentrate is applied in undiluted form or diluted with water to form an oil-in-water emulsion; The above uses.

Claims

1. Allyl isothiocyanate At least one vegetable oil esterified with a C1 to C6 alkyl group At least one nonionic surfactant At least one anionic surfactant Including, An agrochemical emulsifiable concentrate, wherein the vegetable oil is selected from rapeseed oil, soybean oil, olive oil, castor oil, and linseed oil.

2. An agrochemical emulsifiable concentrate as described in claim 1, wherein the at least one esterified vegetable oil is a methyl ester of rapeseed oil fatty acid.

3. 3. An agrochemical emulsifiable concentrate according to claim 1 or claim 2, wherein the allyl isothiocyanate is present in an amount ranging from 1% to 70% by weight based on the weight of the emulsifiable concentrate.

4. An agrochemical emulsifiable concentrate according to any one of claims 1 to 3, wherein the allyl isothiocyanate is present in an amount ranging from 5% to 45% by weight based on the weight of the emulsifiable concentrate.

5. 5. An agrochemical emulsifiable concentrate according to any one of claims 1 to 4, wherein the at least one esterified vegetable oil is present in an amount ranging from 1% to 90% by weight based on the weight of the emulsifiable concentrate.

6. An agrochemical emulsifiable concentrate as described in claim 5, wherein the at least one esterified vegetable oil is present in an amount within the range of 40% to 70% by weight based on the weight of the emulsifiable concentrate.

7. 7. The agrochemical emulsifiable concentrate according to any one of claims 1 to 6, wherein the at least one nonionic surfactant is selected from the group consisting of ethoxylated block copolymers, eth-propoxylated block copolymers, ethoxylated tristyrylphenol, eth-propoxylated tristyrylphenol, ethoxylated tristyrylphenol phosphate (acid form), ethoxylated tristyrylphenol sulfate (acid form), sorbitan monolaurate, ethoxylated sorbitan monolaurate, sorbitan monooleate, ethoxylated sorbitan monooleate, ethoxylated vegetable oils, ethoxylated fatty alcohols, organosilicon compounds, and mixtures thereof.

8. 8. An agrochemical emulsifiable concentrate according to any one of claims 1 to 7, wherein said at least one nonionic surfactant is present in said emulsifiable concentrate in an amount in the range of 1% to 20% by weight, based on the weight of said emulsifiable concentrate.

9. 9. An agrochemical emulsifiable concentrate according to any one of claims 1 to 8, wherein said at least one anionic surfactant is selected from ethoxylated tristyrylphenol phosphate (salified form), ethoxylated tristyrylphenol sulfate (salified form), calcium dodecylbenzene sulfonate, and mixtures thereof.

10. 10. An agrochemical emulsifiable concentrate according to any one of claims 1 to 9, wherein the at least one anionic surfactant is present in the emulsifiable concentrate in an amount ranging from 1% to 20% by weight, based on the weight of the emulsifiable concentrate.

11. (as weight percent based on weight of emulsifiable concentrate) 5% to 45% by weight of allyl isothiocyanate 5% to 15% by weight of at least one nonionic surfactant 1% to 10% by weight of at least one anionic surfactant said at least one esterified vegetable oil in an amount equal to the remainder necessary to bring the weight of said emulsifiable concentrate to 100% by weight; 2. The agrochemical emulsifiable concentrate of claim 1, comprising:

12. Providing at least one agrochemical emulsifiable concentrate according to claim 1; diluting said emulsifiable concentrate with water to obtain an agricultural formulation in the form of an oil-in-water emulsion; 1. A process for preparing an agricultural formulation in the form of an oil-in-water emulsion, comprising:

13. 10. The method of claim 1, further comprising applying to a crop plant at least one effective dose of the agrochemical emulsifiable concentrate of claim 1, The emulsifiable concentrate is applied in undiluted form or in the form of dilution with water to form an oil-in-water emulsion; A method for controlling nematodes in crop plants.

14. 2. Use of an agrochemical emulsifiable concentrate according to claim 1 as a nematicide in crop plants, comprising: The emulsifiable concentrate is applied in undiluted form or in the form of dilution with water to form an oil-in-water emulsion; The above uses.

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