JPWO2020102232A5 - - Google Patents

Description

(Cross reference to related applications)
This international application claims priority to U.S. Provisional Application No. 62/760,565, filed November 13, 2018, which is expressly incorporated herein by reference in its entirety.

(Field of invention)
The technical field to which this invention generally pertains is products useful in fungicidal, insecticidal, and herbicidal compositions and methods of making such products.

Many chemical products are known to be very useful as materials for herbicidal and insecticidal applications, but due to the complexity of such products, e.g. to improve their stability and dispersibility. There is a constant search for ways to improve the efficiency and effectiveness of.

The figure depicts a representative complex coacervation process for manufacturing the products described herein.

A composition specifically adapted for herbicidal applications is disclosed, the composition comprising microcapsules containing one or more biopolymers and one or more cyclohexanedione-based compounds encapsulated therein. This results in improved chemical stability and dispersibility of the cyclohexanedione-based compound suitable for the application.

Further embodiments include a composition as described above wherein the cyclohexanedione-based compound comprises clethodim; a composition as described above wherein the biopolymer comprises a polysaccharide and/or cellulose; a composition as described above wherein the polysaccharide comprises inulin; A composition as described above comprising a surfactant, a composition as described above in which the cyclohexanedione compound is present in the microcapsules in an amount of 1% to 70% by weight, a composition as described above produced by complex coacervation, a composition as described above. The composition as described above, wherein the product optionally contains one or more of natural rubber, starch, protein, alcohol, water-soluble polymer, and/or oil, wherein the alcohol comprises sorbitol; Compositions as described above comprising gum arabic, compositions as described above in which the surfactant comprises one or more polyalkylene oxide block copolymers, aqueous dispersions containing the compositions as described above, and oil dispersions containing the compositions as described above. a composition as described above, wherein the oil comprises a vegetable oil; a composition as described above, wherein the oil comprises soybean oil, pine oil, and/or sunflower oil; a composition as described above, wherein the oil comprises a paraffinic oil; the oil comprises an aromatic solvent; wherein the solvent comprises a C ₉ -C ₁₀ dialkyl and trialkylbenzene (such as Aromatic 100, Aromatic 150, or Aromatic 200), wherein the vegetable oil comprises rapeseed oil/or methylated rapeseed oil. composition, the oil is polyoxyethylene sorbitan monolaurate having a carbon chain length in the range of C ₁₀ to C ₂₀ (e.g. Tween 80 or Tween 20 or Tween 85 or Tween 60 (Sigma-Aldrich), wherein the polyoxyethylene sorbitan is a monolaurate, monostearate, tristearate, and/or trioleate.

A method of controlling insects and/or weeds is also described comprising applying the above composition.

Additional embodiments described include methods of performing the application step as a post-emergence step after the crop germinates, and methods of performing the application step as a pre-emergence step before the crop germinates.

These and further embodiments will become apparent from the description below.

The details set forth herein are by way of example only and for the purpose of illustrative elaboration of various embodiments of the invention, and are intended to illustrate the most useful and easily understood principles and conceptual aspects of the invention. It is presented to provide what is considered to be an explanation. In this regard, no attempt has been made to describe the invention in more detail than is necessary for a basic understanding of the invention, but this disclosure will make it clear to those skilled in the art that several forms may be implemented in practice. to reveal.

The invention will now be described with reference to more detailed embodiments. However, this invention may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in describing the invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in the description of the invention and the appended claims, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise. is intended. All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety.

Unless stated otherwise, all numbers expressing amounts of components, reaction conditions, etc. used in the specification and claims are to be understood as modified in all cases by the term "about" Should. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the invention. At a minimum, no attempt should be made to limit the application of the doctrine of equivalents to the claims, and the value of each numerical parameter should be construed in light of the number of significant digits and conventional rounding techniques.

Notwithstanding that numerical ranges and parameters indicating the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently includes certain errors that necessarily result from the standard deviation found in each test measurement. Every numerical range given throughout this specification includes every narrower numerical range that falls within the broader numerical range, as if all narrower numerical ranges were expressly written herein.

Further advantages of the invention will be set forth in part in the following description, and in part will be obvious from the description or can be learned by practice of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claimed invention.

Described herein is the encapsulation of cyclohexanedione-based compounds to improve both their chemical stability and dispersibility, including inter alia with other premix molecules and different mixtures. These include improved compatibility, sustainable release, extended release profiles, and longer crop protection. Through the use of biopolymer encapsulating materials (eg, polysaccharides and cellulose, see also Table), microcapsules of cyclohexanedione-based compounds (eg, clethodim, etc.) are formed by conventional complex coacervation techniques. However, through this encapsulation technique and careful selection of one or more appropriate surfactants, the new delivery system exhibits a number of advantages, including some examples listed below: Significant chemical stability (e.g. , in the case of clethodim, compared to currently available clethodim products, the stability of microcapsules after degradation under accelerated temperature conditions (at 54 °C for at least 2 weeks) either in dry form or in oil dispersion (e.g. , in the case of clethodim products), in dry form or in oil dispersion for the purpose of high dispersion of the microcapsules in either the aqueous or oil phase, controlled release of the encapsulated active ingredient, formulation volume useful for the particular application method. Significantly higher loading of the active ingredient either in the liquid state and the action of the oil phase as an incorporated adjuvant to improve the bioavailability of the oil dispersion.

A representative complex coacervation process using appropriate surfactants selected is described below. See also figure. The ingredients of the composition are first hydrated and thoroughly mixed (1). The solution contains the materials of the composition at a concentration of 2% to 50% by weight, based on their molecular weight and the desired viscosity of the final solution, i.e., an equilibrium viscosity to minimize product handling and phase separation. It is prepared by dispersing it in The solution is gently stirred and stored, eg, overnight, to ensure complete hydration of the biopolymer (2). If necessary, heat may be applied to improve solubility. The biopolymer solution or mixture of biopolymer solutions is mixed in a beaker containing a suitable surfactant (3). A clethodim solution with a concentration of 50% to 80% was then weighed into a beaker (4) and homogenized for 10 minutes with a conventional stirrer at 5,000 to 10,000 rpm (5). , to produce a microemulsion. The microemulsion mixture is further spray dried (6) with an air stream having an inlet temperature of 110°C to 120°C. The microcapsule powder is collected and analyzed.

Alternatively, the microcapsule powder can be further made into an oil dispersion by suspending the powder in one or more selected oils at a concentration of 20% to 90% under stirring. Optionally, one or more surfactants, including dispersants, emulsifiers, rheology aids, are added to the oil dispersion to stabilize the mixture. The oil dispersion is analyzed below.

Representative encapsulation efficiencies with various delivery systems are shown below. To determine the total oil content, 0.5 g (gram) of encapsulated powder is mixed with 10 mL (milliliter) of water and stirred for 2 minutes. Add 10 mL of isopropanol and hexane (1:1 to 1:3 ratio) and stir for 5 minutes. The solution is then centrifuged, filtered and placed in a 70°C water bath to evaporate the solvent. Record the final weight of oil. To determine surface oil content, 0.5 g of encapsulated powder is mixed with hexane, centrifuged and filtered. Evaporate the supernatant as above and record the amount of oil. The results are shown in Table 1 below.

The chemical retention of encapsulated clethodim powder stored at 54°C is compared to currently commercially available EC (emulsifiable concentrate) products.

The chemical retention of encapsulated clethodim oil dispersions stored at 54°C is shown in Table 3.

Dispersibility in 2.5% OD (oil dispersion) diluted in an ASTM 100 ml graduated centrifuge tube is shown in Table 4.

Representative water emulsion compositions (before spray drying) are shown in Tables 5 and 6. Typical compositions of encapsulated powders for suspension in oil to form oil dispersions are shown in Table 7.

As indicated by the table above, the aqueous dispersion may contain functional materials such as: cyclohexanedione-based compounds such as clethodim, polysaccharides such as inulin, natural gums such as gum arabic, maltodextrin, etc. Polysaccharides, starches and polysaccharides such as waxy maize starch, proteins such as whey protein, sugar alcohols such as sorbitol and mannitol, polysaccharide starches, cyclic oligosaccharides such as cyclodextrins; conventional surfactants, e.g. monolauric acid Polyoxyethylene (20) sorbitan, alkylated vinyl pyrrolidone polymer, isopropyl alcohol, EO/PO (ethylene oxide/propylene oxide) block copolymer, anionic polymer dispersant polyalkylene oxide block copolymer, nonionic block copolymer, butyl block copolymer, and polyvinylpyrrolidone water-soluble polymer.

As also shown in the table above, the oil-based dispersion includes EO/PO (ethylene oxide/propylene oxide) block copolymer, polyalkylene oxide block copolymer, EO/PO block copolymer, nonionic block copolymer, butyl block copolymer, Polyvinylpyrrolidone water-soluble polymer, anionic polymer dispersant, cetyl ether phosphate, oleyl ether phosphate, polyoxyethylene (5) oleyl mono/diphosphate, polyoxyethylene (3) oleyl mono/diphosphate, dioctyl sodium sulfosuccinate, hexaoleic acid Functional materials such as conventional surfactants such as polyoxyethylene (40) sorbitol, ethoxylated castor oil and rapeseed oil fatty acid methyl esters may also be included.

These examples are illustrative only and are not to be understood as limiting the scope or underlying principles of the invention in any way. Various modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art after reviewing the following examples and the foregoing description. Such modifications are also intended to be included within the scope of the appended claims.

As described herein, these and other problems in this area are addressed by the invention described herein. It is therefore intended that the scope of the invention include all modifications and variations that may fall within the scope of the appended claims. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be regarded as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims (19)

A composition for herbicidal use, comprising a cyclohexanedione compound encapsulated in biopolymer microcapsules, the cyclohexanedione compound comprising clethodim, and the biopolymer comprising inulin and/or cellulose. 2. The composition of claim 1, further comprising a surfactant. The composition of claim 1, wherein the cyclohexanedione-based compound is present in the microcapsules in an amount of 1% to 70% by weight. 2. The composition of claim 1, wherein the composition optionally contains natural gum, starch, protein, alcohol, water-soluble polymer, and/or oil. 5. The composition of claim 4, wherein the alcohol comprises sorbitol. 5. The composition of claim 4, wherein the natural rubber comprises gum arabic. 3. The composition of claim 2, wherein the surfactant comprises one or more polyalkylene oxide block copolymers. An aqueous dispersion containing the composition according to claim 1. An oil dispersion containing the composition according to claim 1. The oil dispersion according to claim 9, wherein the oil comprises a vegetable oil. Oil dispersion according to claim 9, wherein the oil comprises soybean oil, pine oil and/or sunflower oil, rapeseed oil and/or methylated rapeseed oil. The oil dispersion according to claim 9, wherein the oil comprises a paraffinic oil. The oil dispersion according to claim 9, wherein the oil contains an aromatic solvent. 14. The oil dispersion of claim 13, wherein the solvent comprises _C9 - _C10 dialkyl and trialkylbenzenes. An oil dispersion according to claim 9, wherein the oil comprises a fatty acid ester of polyoxyethylene sorbitan having a carbon chain length in the range of C ₁₀ to C ₂₀ . The oil dispersion according to claim 15, wherein the fatty acid ester is a monolaurate, monostearate, tristearate, and/or trioleate. A method for controlling insects and/or weeds contained in crops, which comprises applying the composition according to any one of claims 1 to 7 to crops. 18. The method of claim 17, wherein the applying step is carried out as a post-emergence step after the crop has germinated. 18. The method of claim 17, wherein the applying step is carried out as a pre-emergence step before the crop germinates.