Chemical composition stabilized by cellulose nanocrystals

Abstract

FIELD: agriculture.SUBSTANCE: liquid pest control composition comprises: a first phase; a second phase that is immiscible with the first phase and dispersed therein; a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and at least one agrochemically active ingredient in the second phase. A liquid composition for regulating plant growth comprises: a first phase; a second phase, which is immiscible with the first phase and dispersed therein; a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and at least one agrochemically active ingredient in the second phase. A method for controlling infestation of plant species by pests by diluting an effective amount of a concentrated composition with an aqueous liquid carrier selected from water and a liquid fertilizer or a combination thereof, and applying the diluted composition to the plant species or their growing site. A method for regulating plant growth by diluting an effective amount of a concentrated composition with an aqueous liquid carrier selected from water and a liquid fertilizer or a combination thereof, and applying the diluted composition to plant species or their growing site. A method for producing a liquid composition comprises: dissolving or suspending an agrochemically active ingredient in the second phase; incorporating cellulose nanocrystals into the first phase, or the second phase, or both; combining the first phase and the second phase to form a composition; shaking the composition to form an emulsion; and cross-linking the cellulose nanocrystals to form a matrix shell around droplets of the second phase. A plant seed covered with a composition.EFFECT: making biodegradable compositions.19 cl, 6 dwg, 13 tbl, 7 ex

Description

[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 63 / 262,525, filed October 14, 2021, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present invention relates to stabilized liquid chemical compositions, the preparation of such compositions and a method of using such compositions, for example, for pest control or as plant growth regulators.BACKGROUND OF THE INVENTION

[0003] In general, modern agrochemical encapsulation technology is based on the formation of polyurea walls through a condensation reaction of isocyanate monomer building blocks. The use of such compounds results in the release of microplastics, which are not particularly biodegradable and can persist in the environment for many years. Accordingly, there is a need for biodegradable alternatives. SUMMARY OF THE INVENTION

[0004] These and other problems are solved by using cellulose nanocrystals (“CNC”) in agrochemical formulations.

[0005] The present invention provides a liquid composition comprising a first phase, a second phase that is immiscible with the first phase and dispersed therein, a matrix based on cross-linked cellulose nanocrystals at the interface between the first and second phases, and at least one agrochemically active ingredient in the second phase.

[0006] The present invention provides a method that comprises obtaining a first phase, obtaining a second phase, dissolving or suspending an agrochemically active ingredient in the second phase, incorporating cellulose nanocrystals into the first phase or the second phase, or both, combining the first phase and the second phase to form a composition, shaking the composition to form an emulsion, and crosslinking the cellulose nanocrystals to form a matrix shell around droplets of the second phase.

[0007] The invention provides an industrial product containing a plant seed coated with a first phase, a second phase that is immiscible with the first phase and dispersed in it, a matrix based on cross-linked cellulose nanocrystals at the interface between the first and second phases, and at least one agrochemically active ingredient in the second phase. BRIEF DESCRIPTION OF GRAPHIC MATERIALS

[0008] Fig. 1 is an image of the crosslinked and non-crosslinked CNC-based composites after two weeks of thermal cycling.

[0009] Fig. 2 is a microscopic image of the cross-linked and non-cross-linked CNC-based composites after drying.

[0010] Fig. 3 is a graph of the release rate of dimethyl phthalate from cross-linked and non-cross-linked CNC formulations.[OOP] Fig. 4 is a graph of the release rate profiles of lambda-cyhalothrin.

[0012] Fig. 5 is a graph of additional release rate profiles of lambda-cyhalothrin.

[0013] Fig. 6 is a graph of the release rate profiles of lambda-cyhalothrin after two weeks of storage at 25°C or 54°C. DETAILED DESCRIPTION OF THE INVENTION

[0014] In embodiments of the present invention, CNC is used to stabilize and / or encapsulate agrochemicals in formulations. CNC is used in Pickering emulsions as colloidal particles to stabilize the oil-water interface. See U.S. Patent No. 9,260,551, incorporated herein by reference.

[0015] CNCs are particularly unique in the field of emulsion stabilization due to their amphiphilic nature, which is due to their long-range ordered crystalline structure. This structure allows hydrophilic hydroxyl groups to be located on one surface and hydrophobic alkyl groups to be located on the adjacent surface. This feature allows CNCs to wet the interface between aqueous and non-aqueous media, producing a stabilized Pickering emulsion system.

[0016] Furthermore, the relatively high aspect ratio of CNCs, which have needle- or rod-like structures, is also beneficial for emulsion stability. Cellulosic materials are used as reference materials for microbial biodegradation studies, so their use as Pickering stabilizers offers numerous advantages in terms of physical stability and encapsulation of agriculturally active ingredients, while also providing an interfacial matrix that is environmentally friendly and readily biodegradable in soil.

[0017] In the present invention, the source and / or polymorph of CNCs is not limited. Any CNCs, both synthetic and naturally occurring, can be used in embodiments of the present invention. Furthermore, CNCs can be obtained from naturally occurring biomaterials, such as hardwood and softwood pulp, non-wood waste, tunicates, and bacteria, as well as from other sources. The starting materials can be separated into individual fibers from macrostructures and, ultimately, into crystalline cellulose domains using a combination of conventional mechanical and chemical processing methods.

[0018] In general, CNCs will be characterized by a needle-shaped or elongated shape. Such elongated or needle-shaped shapes can be considered in terms of two dimensions, characterized by length and width. In the context of needle-shaped shapes, width refers to the maximum width of the needle. In certain embodiments, CNCs are characterized by a width of 1-50 nm. In preferred embodiments, the width is 4-25 nm. Therefore, it follows that the width value may be approximately any value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 nm, or may be in any range in which these width values ​​are indicated. In other embodiments, the CNC may have a length of 50-1000 nm. In preferred embodiments, the length is 100-400 nm.It follows that the length value may be approximately any value from 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990 or 1000 nm or may be in any range in which these length values ​​are designated or between such length values.

[0019] In some embodiments, CNCs may be defined in terms of dimensions, i.e., aspect ratio. Aspect ratio is defined as the ratio of width to length. CNCs may have an aspect ratio of 1:2 to 1:200. In preferred embodiments, the aspect ratio is from 1:20 to 1:80. It follows that the width value may be approximately any value from 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49 and 1:50, or may be in any range in which these aspect ratios are designated.

[0020] The size and dimension values ​​of the CNCs used in the composition may be characterized by a Gaussian distribution shape. In specific embodiments, the CNCs may be characterized by some multimodal distribution.Multimodal distributions include bimodal, trimodal, and higher order distributions. The standard deviation value may vary depending on a particular parameter; for example, the standard deviation value for width may be 0.1, 1, 2, 3, 5, or 10 nm, or a range between them. Alternatively, the standard deviation value for length may be 1, 5, 10, 25, 50, 100, 250, or 500 nm, or a range between them. In some embodiments, the standard deviation value for aspect ratio length may be ±1, ±2, ±3, ±5, ±10, or ±20, or a range between them.

[0021] Depending on the embodiment, CNCs make up approximately 0.1-3% w / w of the total weight of the composition. In preferred embodiments, the amount of CNCs is 0.5-1.5% w / w. It follows that the value of the total amount of CNCs in the composition can be approximately any value of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0, or be in the range between them. In some embodiments, CNCs may be included in excess. In these embodiments, the total amount of CNCs may be at least about 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% w / w.

[0022] In a particular embodiment, the composition provides a liquid composition comprising a first phase, a second phase that is immiscible with the first phase and dispersed therein, a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase, and at least one agrochemically active ingredient in the second phase.

[0023] In some embodiments, the first phase may be selected such that the agrochemically active ingredient is distributed exclusively or substantially exclusively in the second phase. In such embodiments, the agrochemically active ingredient is not susceptible or substantially not susceptible to migration into the first phase. Those skilled in the art can readily determine whether a particular aqueous liquid meets this criterion for the particular agrochemically active ingredient under consideration by following any standard test procedure for determining the partition coefficient of a compound between the first phase and the second phase.

[0024] In a further embodiment, the first phase is an aqueous liquid or a solution of water-soluble solutes in water.

[0025] Water-soluble solutes suitable for use in the first phase include salts such as halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides, and sulfides of ammonium and metals such as metals of Groups 1–12 of the periodic table. Other suitable solutes include sugars and osmolytes such as polysaccharides, proteins, betaines, and amino acids.

[0026] In one embodiment, aqueous liquids suitable for use in the first phase are mixtures of water and a non-aqueous liquid that is substantially miscible with water. In the context of the present invention, the term "substantially miscible with water" means a non-aqueous liquid that forms a single phase when present in water at a concentration of at least 50% by weight.

[0027] Inherently water-miscible non-aqueous liquids suitable for use in the first phase include, for example, propylene carbonate; a water-miscible glycol selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having a molecular weight of no more than about 800; an acetylated glycol such as dipropylene glycol methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; gamma-butyrolactone; a water-miscible alcohol such as propanol or tetrahydrofurfuryl alcohol; N-methylpyrrolidone; dimethyl lactamide, and mixtures thereof. In one embodiment, the non-aqueous, substantially water-miscible liquid used in the first phase is a solvent for at least one optional agrochemically active ingredient.

[0028] In another embodiment, the aqueous, substantially water-miscible liquid used in the first phase is completely miscible with water in all proportions. Alternatively, the aqueous, substantially water-miscible liquid used in the first phase is a waxy solid, such as polyethylene glycol, characterized by a molecular weight of greater than about 1000, and the mixture of this waxy solid with water is maintained in a liquid state by forming the composition at an elevated temperature.

[0029] In another embodiment, the second phase is a non-aqueous liquid. In another embodiment, the first phase is a substantially water-miscible non-aqueous liquid. The water-immiscible non-aqueous liquid can be selected from petroleum distillates, vegetable oils, silicone oils, methylated vegetable oils, purified paraffinic hydrocarbons, alkyl lactates, mineral oils, alkyl amides, alkyl acetates, and mixtures thereof.

[0030] In another embodiment, the first phase comprises a substantially water-miscible non-aqueous liquid. The water-miscible non-aqueous liquid can be selected from the group consisting of propylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, polyethylene glycols having a molecular weight of no more than about 800, di(propylene glycol) methyl ether acetate, propylene glycol diacetate, triethyl phosphate, ethyl lactate, gamma-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyl lactamide and mixtures thereof.

[0031] Those skilled in the art will appreciate that the amounts of water and the nature and amount of the non-aqueous, water-miscible liquid or water-soluble solute can be easily varied to obtain mixed aqueous liquids suitable for use in the first phase, and these amounts can be easily determined without undue experimentation.

[0032] The second phase is selected to be immiscible with the first phase. The second phase may be selected independently of the first phase, or the first phase may be selected independently of the second phase. Furthermore, both the first and second phases may be selected based on the physical properties of the selected agrochemically active ingredient to achieve appropriate suspension or solvation.

[0033] In preferred embodiments, the second phase is a non-aqueous solvent or oil, such as, but not limited to, alkylated aromatic carboxylic acids (acetophenone, benzyl benzoate, butyl benzoate); tris(2-ethylhexyl)phosphate; fatty acid oils (stearic acid, linoleic acid, oleic acid, canola oil, rapeseed oil, soybean oil); alkylated fatty acid oils (e.g., methylated rapeseed oil, methyl oleate, methylated soybean oil); aromatic hydrocarbons; diisononyl ether of cyclohexane-1,2-dicarboxylic acid; petroleum distillates (including mineral oils); alkylated pyrolidones; simple chain alkanes (e.g., heptane, dodecane, hexadecane and their isomers) and fatty alcohols (octanol, stearyl alcohol, oleyl alcohol).

[0034] Depending on the embodiment, the first phase can make up 50-90% w / w of the composition, while the second phase can make up 10-50% w / w of the composition. In certain embodiments, the second phase is any amount of 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, and 50%, or values ​​in amounts and ranges between them.

[0035] In general, a matrix based on crosslinked CNCs at the interface between a first phase and a second phase is formed by dispersing CNCs in the first phase or the second phase, combining the first phase and the second phase, mixing and / or shaking the first phase and the second phase so that the second phase is dispersed in the first phase, and then crosslinking the CNCs.

[0036] In certain embodiments, salts can be used to modulate the surface charge density on the CNC surface as needed to ensure maximum coverage of the droplet surface by the CNC. Specific salts include, but are not limited to, monovalent and polyvalent metal halides, such as NaCl or CaCl2, or organic salt derivatives, such as (NH4)2SO4. The salt concentration can be from 0.001 to 0.1 M. These salts can be present before crosslinking or in the final composition. In certain embodiments, the amount of salt is 0.001, 0.005, 0.01, 0.05, or 0.1, or values ​​in amounts and ranges therebetween.

[0037] Surfactants may additionally be included to ensure particle size uniformity and stability. The surfactant may be selected based on the specific first phase and second phase or the active substances contained therein. In general, the amount of surfactant may range from about 0.01 to 5% w / w. In certain embodiments, the surfactant is sodium dodecyl sulfate. Certain embodiments relate to solvent-free formulations.

[0038] Certain embodiments of the present invention relate to compositions in which the interface between the first phase and the second phase is covered by CNC by 30-100%. A coverage of 100% corresponds to solid matrices. In particular embodiments, the interface is covered by CNC by at least 60%. In other embodiments, the interface is covered by CNC by 50-80%. CNC coverage can be approximately 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, or values ​​in amounts and ranges therebetween.

[0039] CNC can be crosslinked using any technique known in the art. Preferred methods for achieving crosslinking include chemical and physical crosslinking using polyaldehydes, polyphenols, polyamines, or polycarboxylic acids. Specific crosslinking agents include glutaraldehyde, citric acid, tannic acid, and boric acid. Preferred crosslinking agents include glutaraldehyde and citric acid.

[0040] Other crosslinking methods can occur by exploiting ionic interactions between CNC particles using various polyvalent metals and their corresponding salts, common examples include but are not limited to Mg(II), Ca(II), Fe(III), Cu(II), Zn(II) or Al(III) salts.

[0041] The amount of crosslinking agent used may depend on the specific crosslinking agent. In general, the amount of crosslinking agent may be greater than 0.01% w / w, in some embodiments, the crosslinking agent is present in an amount of 0.01 to 10% w / w. In preferred embodiments, the crosslinking agent is present in an amount of 0.01 to 5% w / w. In some embodiments, the amount of crosslinking agent is 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% weight / weight or values ​​in amounts and ranges therebetween.

[0042] In specific embodiments, the second phase comprises droplets with a diameter of 1-100 microns. In preferred embodiments, the droplet size is 1-30 microns. The diameter can be defined as the average diameter size. Therefore, the diameter can be 1, 1.5, 2, 2.5, or 3 microns, or values ​​in amounts and ranges between them. In specific embodiments, the diameter is less than 10 microns, less than 5 microns, less than 3 microns, less than 2 microns, less than 1 micron, or less than 0.5 microns.

[0043] In some embodiments, the composition and droplets may be determined based on their properties, such as the release rate of agrochemicals or storage stability.

[0044] In some embodiments, the release rate is defined as the rate at which the agriculturally active ingredient diffuses through the interfacial matrix into the surrounding medium, such as soil, leaf surfaces, or a solvent reservoir. For quantitative determination, release rate tests can be performed to compare the rate at which the active ingredient diffuses through the interfacial matrix with that of other formulations. Without being limited by theory, modifications such as cross-linking can modulate the release rate, resulting in capsules with either delayed or rapid release, based on the percentage of release over time. Both rapid- and slow-release capsules are advantageous for agricultural pesticide products and are targeted using this technology.In some embodiments, the maximum release of the agriculturally active ingredient payload is achieved within 1, 2, 3, 4, 5, 6, 12, or 24 hours after application. In other embodiments, the maximum release of the agriculturally active ingredient payload is achieved within 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 days after application.

[0045] In some embodiments, shelf stability is defined as the ability of a formulated product to remain physically and chemically stable for at least a 2-year shelf life. This can be achieved through extended storage at low, ambient, or high temperatures, as well as through thermal cycling procedures to simulate the aging process. Physical stability refers to the ability of the formulation to resist emulsion breakdown due to coalescence, Ostwald ripening, flocculation, layer separation, phase separation, or other physical changes such as thickening or sedimentation. Additionally, chemical stability refers to the ability of the formulated product to resist chemical degradation of the agriculturally active ingredients contained in the formulation.Typically, acceptable tolerances for active ingredient degradation are ±10% for loadings of 0-1 wt%, ±5% for loadings of 1-20 wt%, and ±3% for loadings greater than 20 wt% during these simulated storage conditions.

[0046] The term "agrochemically active ingredient" means chemical substances and biological compositions, such as those described herein, that are effective in killing, preventing, or controlling the growth of unwanted agricultural pests such as plants, insects, mice, microorganisms, algae, fungi, bacteria, and the like (e.g., pesticide active ingredients). This term can also be applied to compounds that act as adjuvants to promote the uptake and delivery of other active compounds. The term can also be applied to compounds that control plant growth in a desired manner (e.g., plant growth regulators), to a compound that mimics the activated natural systemic resistance response found in plant species (e.g., plant activator), or to a compound that reduces the phytotoxic response to herbicides (e.g., safener).Where more than one agrochemically active ingredient is present, they are independently present in an amount that is biologically effective when the composition is diluted, if necessary, in a suitable volume of liquid carrier, such as water, and applied to the intended target, such as the foliage of a plant or its growing site.

[0047] Examples of agrochemically active ingredients suitable for use, in addition to their enantiomers, are, without limitation, the following: fungicides such as azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidin, fludioxonil, mandipropamide, mefenoxam, paclobutrazol, picoxystrobin, propiconazole, pyraclostrobin, sedaxan, tebuconazole, thiabendazole and trifloxystrobin; Herbicides such as acetochlor, alachlor, ametryn, anilofos, atrazine, azaphenidine, benfluralin, benfuresate, bensulide, benzphenedizone, benzofenap, bicyclopyrone, bromobutide, bromofenoxime, bromoxynil, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chloridazone, chlorpropham, chlorthal-dimethyl, chlorthiamide, cinidon-ethyl, cinmethylin, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, desmedipham, desmethrine, dichlobenil, diflufenican, dimepiperate, dimetachlor, dimetamethrin, dimethenamid, dimethenamid-R, dinitramine, dinoterb, diphenamide,dithiopyr, ERTCS, esprocarb, etalfluralin, ethofumesate, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, flamprop-methyl, flamprop-M-isopropyl, fluazolate, fluchloralin, flufenacet, flumiclorax-pentyl, flumioxazine, flurochloridone, flupoxam, flurenol, fluridone, flurtamone, fluthiacet-methyl, indanophan, isoxaben, isoxaflutole, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, metabenzthiazuron, methyldimron, metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, molinate, naproanilide, napropamide, neburon, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazone, oxyfluorfen, pebulate, pendimethalin, pentanochlor, pentaxamide, pentoxazone, phenmedipham, pinoxaden, piperophos, pretilachlor, prodiamine, profluazol, prometon, promethrin, propachlor, propanil, propazine, propham, propisochlor, propizamide, prosulfocarb, pidiflumethofen, pyraflufen-ethyl, pyrazogyl, pyrazolinate, pyrazoxifene, piributicarb, pyridate, pyriminobac-methyl, quinclorac, siduron, simazine, symetryn,S-metolachlor, sulcotrione, sulfentrazone, tebutam, tebuthiuron, terbacil, terbumetone, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thidiazimine, thiobencarb, thiocarbazil, triallate, triethazine, trifluralin, and vernolate; herbicide safeners such as benoxacor, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr; the alkali metal, alkaline earth metal, sulfonium, or ammonium cation of mefenpyr; mefenpyr-diethyl, and oxabetrinil; Insecticides such as abamectin, clothianidin, cyantraniliprole, cyantraniliprole, emamectin benzoate, gamma-cyhalothrin, imidacloprid, cyhalothrin and its enantiomers such as lambda-cyhalothrin, tefluthrin, permethrin, resmethrin and thiamethoxam; nematicides such as fosthiazate, fenamiphos and aldicarb.

[0048] In one embodiment, any active ingredients in the second phase may be in the form of a solution or a suspended particle. Additionally, any active ingredients contained in the first phase may be in the form of a solution or suspended particles.

[0049] Additional aspects of the present invention include a method for preventing or controlling the infestation of plant species by pests and regulating plant growth by diluting an amount of a concentrate composition with a suitable liquid carrier, such as water or liquid fertilizer, and applying it to a plant, tree, animal, or habitat as needed. The compositions of the present invention can also be combined with water in a continuous flow device in spray application equipment, eliminating the need for a storage tank for the diluted product.

[0050] The compositions of the present invention can be conveniently stored in a container from which they are poured or pumped, or into which a liquid carrier is added before use.

[0051] As used in this document, the term "agrochemically effective amount" means the amount of an agrochemically active compound that provides negative regulation or modification of target pests or provides plant growth regulation (PGR). For example, in the case of herbicides, the "herbicidally effective amount" is the amount of the herbicide that is sufficient to provide control or modification of plant growth. Effects with respect to control or modification include all deviations from natural development, such as killing, growth inhibition, leaf scorch, albinism, dwarfing, etc. The term "plants" refers to all physical parts of the plant, including seeds, seedlings, shoots, roots, tubers, stems, stipes, foliage, and fruits. In the case of fungicides, the term "fungicide" shall mean a substance that kills or substantially inhibits the growth, proliferation, division, reproduction, or dissemination of fungi.As used herein, the term "fungicidally effective amount" or "amount effective to control or reduce fungi" with respect to a fungicidal compound means an amount that will kill or substantially inhibit the growth, proliferation, division, reproduction, or spread of a significant number of fungi. As used herein, the terms "insecticide," "nematicide," or "acaricide" shall mean a substance that kills or substantially inhibits the growth, proliferation, reproduction, or spread of insects, nematodes, or mites, respectively. An "effective amount" of an insecticide, nematicide, or acaricide means an amount that ensures the killing or substantially inhibition of the growth, proliferation, reproduction, or spread of a significant number of insects, nematodes, or mites.

[0052] In one aspect, when used herein, "plant growth regulation," "plant growth regulator," PGR, "regulation," or "regulating" include the following plant responses: inhibiting cell elongation, such as reducing stem height and internodal spacing, strengthening stem walls to increase lodging resistance, compact growth of ornamental plants to economically produce improved quality plants, promoting better fruiting, increasing the number of ovaries to increase yield, promoting senescence of tissue formation to allow fruit to fall off; defoliation of planting material and ornamental shrubs and trees for mail order in the fall, defoliation of trees to disrupt parasitic infection chains, accelerating ripening for the purpose of crop planning by reducing the yield to one or two harvests, and disrupting the food chain of harmful insects.

[0053] In another aspect, "plant growth regulation," "plant growth regulator," "PGR," "regulation," or "regulation" also includes the use of a composition according to the present invention to increase the yield and / or improve the vitality of an agricultural plant. According to one embodiment of the present invention, the compositions of the present invention are used to increase the resistance to stress factors such as fungi, bacteria, viruses, and / or insects, and stress factors such as heat stress, nutrient stress, cold stress, drought stress, UV stress, and / or salt stress in an agricultural plant.

[0054] Selecting application rates associated with achieving the desired level of pesticidal activity of the composition of the present invention is a routine procedure for those skilled in the art. Application rates will depend on factors such as pest pressure, plant condition, weather, and growing conditions, as well as the potency of the agrochemically active ingredients and any relevant rate limitations on the label.

[0055] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, flowers, stalks, leaves, and fruits. The term "habitat" refers to the location where the plant grows or is intended to grow.

[0056] The composition according to the present invention is suitable for all application methods commonly used in agriculture, such as pre-emergence application, post-emergence application, post-harvest application, and seed treatment. The compositions according to the present invention are suitable for pre- and post-emergence application to cultivated crop areas.

[0057] The compositions according to the present invention are also suitable for controlling and / or preventing pests in agricultural crops of useful plants or for regulating the growth of such plants. In some embodiments, the compositions can be applied by any method commonly used, including spraying, dripping, and soaking.

[0058] Preferred agricultural crops of useful plants include corn, canola, cereals such as barley, oats, rye, and wheat, cotton, soybeans, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs, and turf. The components used in the composition of the present invention can be applied in various ways known to those skilled in the art at varying concentrations. The rate at which the composition is applied will depend on the specific type of pest to be controlled, the degree of control required, and the timing and method of application.

[0059] It should be understood that agricultural crops also include those agricultural crops that have been made tolerant to herbicides or classes of herbicides (e.g., ALS, GS, EPSPS, PPO, ACCase, and HPPD inhibitors) by conventional breeding methods or by genetic engineering. An example of an agricultural crop that has been made tolerant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® canola. Examples of agricultural crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-resistant maize varieties commercially available under the trademarks RoundupReady® and LibertyLink®.

[0060] Agricultural crops should also be understood as those that have been given resistance to harmful insects through genetic engineering, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton boll weevil), and Bt potato varieties (resistant to the Colorado potato beetle). Examples of Bt maize include the Bt 176 NK® maize hybrid (Syngenta Seeds). Bt toxin is a protein naturally produced by the soil bacteria Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451878, EP-A-374753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP-A-427529. Examples of transgenic plants containing one or more genes encoding insect resistance and expressing one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato varieties), NatureGard® and Protexcta®.Agricultural crops or their seeds can be both herbicide-resistant and insect-resistant (transgenic objects with "stacked" genes). For example, a seed can express the insecticidal protein Cry3 while being glyphosate-tolerant.

[0061] It should also be understood that agricultural crops include those obtained by conventional breeding methods or genetic engineering and possessing so-called introduced traits (e.g. improved shelf stability, higher nutritional value and improved taste).

[0062] Other useful plants include lawn grass, such as those found on golf courses, lawns, parks and roadsides, or grown commercially for lawns, and ornamental plants such as flowers or shrubs.

[0063] Cultivated areas are areas of land on which cultivated plants are already grown or on which the seeds of these cultivated plants have been sown, as well as areas of land on which it is intended to grow these cultivated plants.

[0064] Other active ingredients such as a herbicide, plant growth regulator, algaecide, fungicide, bactericide, viricide, insecticide, acaricide, nematicide or molluscicide may be present in the formulations of the present invention or may be added to the formulations as a tank mix counterpart.

[0065] The compositions of the present invention may further comprise other inert additives. Such additives include thickeners, anti-caking and anti-caking agents, dispersants, emulsifiers, wetting agents, antifoaming agents, biocides, lubricants, fillers, flow control agents, settling enhancers, excipients, evaporation retarders, anti-freeze agents, insect attractants with a specific odor, UV protection agents, flavoring agents, etc. The thickener may be a compound that can dissolve or swell in water, such as, for example, xanthan polysaccharides (e.g., anionic heteropolysaccharides such as RHODOPOL® 23 (xanthan gum) (Rhodia, Cranbury, NJ)), alginates, guars, or celluloses; synthetic macromolecules such as modified cellulose-based polymers, polycarboxylates, bentonites, montmorillonites, hectonites or attapulgites.The antifreeze agent may be, for example, ethylene glycol, propylene glycol, glycerin, diethylene glycol, sucrose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Illustrative antifoaming agents are silicone oils, polydialkyl siloxanes, in particular polydimethyl siloxanes, fluoroaliphatic esters, or perfluoroalkyl phosphonic / perfluoroalkyl phosphonic acids or their salts and mixtures thereof. Suitable antifoaming agents are polydimethyl siloxanes such as Dow Corning® Antifoam A, Antifoam B, or MSA Antifoam. Illustrative biocides include 1,2-benzisothiazolin-3-one, available under the name PROXEL® GXL (Arch Chemicals).

[0066] Examples of surfactants that can be used include linear and branched alcohol ethoxylates and their acid esters, tristyrylphenol ethoxylates and their acid esters, alkylphenol ethoxylates and their acid esters, linear or branched alkylaryl sulfonates such as dodecylbenzenesulfonate, fatty acid ethoxylates, alkylamine ethoxylates, ethylene oxide block copolymers, and higher alkylene (propylene, butylene) oxides. Examples of non-micellar polymeric dispersants include a homopolymer of polyvinylpyrrolidone with a molecular weight of 15-120 kDa, a random copolymer of polyvinylpyrrolidone and vinyl acetate, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers with an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other conventional non-emulsifying dispersants.

[0067] Dispersing agents are well known in the art and their selection will depend on various factors depending on the given formulation. Preferred dispersing agents, as noted above, include, but are not limited to, a homopolymer of polyvinylpyrrolidone with a molecular weight of 15-120 kDa, a random copolymer of polyvinylpyrrolidone and vinyl acetate, lignosulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers with an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrrolidone and other conventional non-emulsifying dispersing agents.

[0068] The compositions of the present invention can be mixed with fertilizers and still maintain their stability.

[0069] The compositions of the present invention can be applied by conventional agricultural methods. For example, the compositions of the present invention can be mixed with water and / or fertilizers and applied to the desired growing / habitat before and / or after emergence by any method, such as by using aircraft spray tanks, irrigation equipment, direct injection spray equipment, knapsack spray tanks, livestock baths, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), etc. The desired growing / habitat can be soil, plants, etc.

[0070] The technology of the present invention also includes a method of treating seeds or plant parts for vegetative propagation, comprising bringing said seeds or plant parts for vegetative propagation into contact with the composition of the present invention. The technology of the present invention can be applied to a seed or plant part for vegetative propagation in any physiological state at any time between seed collection and seed sowing; during or after sowing; and / or after germination. Preferably, the seed or plant part for vegetative propagation is in a sufficiently stable state that it is not subject to damage or is subject to minimal damage during the treatment, including physical damage or biological damage.The composition can be applied to seeds or plant parts for vegetative propagation using conventional coating or coating techniques and devices, such as fluidized bed techniques, roller mill methods, rotostatic seed dressers, and drum coating machines. Prior to coating, the seeds or plant parts for vegetative propagation can be pre-sorted by size. After coating, the seeds or plant parts for vegetative propagation are typically dried and then transferred to a sorting machine for size sorting. Such procedures are known in the art. In some embodiments, the composition of the present invention is used as a single-ingredient coating for seeds or plant parts for vegetative propagation. Treated seeds can also be coated with a film topcoat to protect the coating.Such top layers are known in the art and can be applied using conventional fluid bed and drum coating techniques, for example.

[0071] Certain embodiments of the present invention are directed to methods for producing a composition. Embodiments of the methods of production include providing a first phase, providing a second phase, dissolving or suspending an agrochemically active ingredient in the second phase, incorporating cellulose nanocrystals into the first phase or the second phase, or both, combining the first phase and the second phase to form a composition, shaking the composition to form an emulsion, and allowing the cellulose nanocrystals to crosslink to form a matrix shell around droplets of the second phase. VARIOUS EMBODIMENTS

[0072] Embodiment 1. A liquid composition comprising: a first phase; a second phase that is immiscible with the first phase and dispersed therein; a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase, and at least one agrochemically active ingredient in the second phase.

[0073] Embodiment 2. The composition according to Embodiment 1, further comprising a dispersing agent.

[0074] Embodiment 3. The composition according to Embodiment 1, wherein the composition does not contain an emulsifying surfactant.

[0075] Embodiment 4. The composition according to Embodiment 1, wherein the cross-linked cellulose nanocrystals are cross-linked with glutaraldehyde.

[0076] Embodiment 5. The composition according to embodiment 1, wherein 40-80% of the interface between the first phase and the second phase is covered with cross-linked cellulose nanocrystals.

[0077] Embodiment 6. The composition according to embodiment 1, wherein the first phase comprises cellulose nanocrystals in an amount sufficient to change the viscosity of the composition by more than 10% compared to a composition that does not contain cellulose nanocrystals in the first phase.

[0078] Embodiment 7. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals are cross-linked with citric acid.

[0079] Embodiment 8. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals are cross-linked with tannic acid.

[0080] Embodiment 9. The composition according to embodiment 1, wherein the first phase comprises water, one or more substantially water-miscible non-aqueous liquids, or a mixture of water and one or more water-miscible liquids.

[0081] Embodiment 10. The composition of embodiment 9, wherein the substantially water-miscible non-aqueous liquid is selected from propylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, hexylene glycol, polyethylene glycols having a molecular weight of no more than about 800, di(propylene glycol), diacetin, triacetin, methyl ether acetate, propylene glycol diacetate, triethyl phosphate; ethyl lactate, gamma-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyl lactamide, and mixtures thereof.

[0082] Embodiment 11. The composition according to embodiment 1, wherein the first phase comprises water and a water-soluble solute.

[0083] Embodiment 12. The composition according to embodiment 11, wherein the water-soluble solute is selected from an acid, a base, a salt, a sugar, a polysaccharide, a protein, an amino acid, a betaine, and mixtures thereof.

[0084] Embodiment 13. The composition according to embodiment 1, wherein the first phase further comprises at least one agrochemically active ingredient, and the active ingredient is in a state selected from a solution or a suspension of particles.

[0085] Embodiment 14. The composition according to embodiment 1, wherein the crosslinked cellulose nanocrystals are crosslinked with boric acid.

[0086] Embodiment 15. The composition according to embodiment 1, wherein the crosslinked cellulose nanocrystals constitute 0.1-5% w / w of the composition.

[0087] Embodiment 16. The composition according to embodiment 1, wherein the crosslinked cellulose nanocrystals constitute approximately 1-2% w / w of the composition.

[0088] Embodiment 17. The composition according to embodiment 1, wherein the crosslinked cellulose nanocrystals constitute approximately 3-5% w / w of the composition.

[0089] Embodiment 18. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals have an aspect ratio of from 1:1 to 1:100.

[0090] Embodiment 19. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals have an aspect ratio of approximately 1:50.

[0091] Embodiment 20. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals are characterized by a width of about 1-100 nm and a length of about 100-1000 nm.

[0092] Embodiment 21. The composition according to Embodiment 1, wherein the crosslinked cellulose nanocrystals are characterized by some multimodal distribution.

[0093] Embodiment 22. The composition according to embodiment 1, wherein the cross-linked cellulose nanocrystals are obtained from microorganisms.

[0094] Embodiment 23. The composition according to Embodiment 1, wherein the cross-linked cellulose nanocrystals are obtained from plant material.

[0095] Embodiment 24. The composition according to embodiment 1, wherein the second phase comprises droplets with a median diameter of from 1 to 100 microns.

[0096] Embodiment 25. The composition according to embodiment 24, wherein the second phase comprises droplets with a median diameter of from 1 to 50 microns.

[0097] Embodiment 26. The composition according to embodiment 25, wherein the second phase comprises droplets with a median diameter of from 1 to 10 microns.

[0098] Embodiment 27. A method for controlling infestation of plant species with pests or regulating plant growth by diluting an effective amount of the concentrated composition according to embodiment 1 with an aqueous liquid carrier selected from water and a liquid fertilizer or a combination thereof, and applying the diluted composition to the plant species or their growing site.

[0099] Embodiment 28. A method comprising: obtaining a first phase; obtaining a second phase; dissolving or suspending an agrochemically active ingredient in the second phase; incorporating cellulose nanocrystals into the first phase or the second phase, or both; combining the first phase and the second phase to form a composition; shaking the composition to form an emulsion and allowing the cellulose nanocrystals to crosslink to form a matrix shell around the droplets of the second phase.

[0100] Embodiment 29. The method according to embodiment 28, wherein crosslinking with glutaraldehyde is provided.

[0101] Embodiment 30. The method according to embodiment 29, wherein crosslinking with citric acid is provided.

[0102] Embodiment 31. The method according to embodiment 28, wherein crosslinking with tannic acid is provided.

[0103] Embodiment 32. The method according to embodiment 28, wherein crosslinking with boric acid is provided.

[0104] Embodiment 33. The method according to embodiment 28, further comprising shaking the first phase and / or the second phase after switching on but before combining.

[0105] Embodiment 34. The method according to embodiment 28, further comprising including a salt in the first phase and / or the second phase.

[0106] Embodiment 35. The method according to embodiment 28, wherein the second phase comprises droplets with a median diameter of from 1 to 100 microns

[0107] Embodiment 36. An industrial article comprising a plant seed coated with the composition according to Embodiment 1.

[0108] Embodiment 37. The article according to claim 36, wherein the composition is dried.

[0109] Embodiment 38. The composition according to embodiment 1, wherein at least one agrochemically active ingredient is characterized by slow release of maximum payload through a matrix based on cross-linked cellulose nanocrystals.

[0110] Embodiment 39. The composition according to embodiment 1, wherein at least one agrochemically active ingredient is characterized by rapid release of the maximum payload through a matrix based on cross-linked cellulose nanocrystals. EXAMPLES

[0111] The following examples further illustrate some aspects of the present invention, but are not intended to limit its scope. Unless otherwise specified in this description and claims, percentages are by weight.

[0112] The composition according to the table above was prepared as follows. NaCl was dissolved in water, then the required amount of solid CNC particles was added and homogenized using high-speed stirring until all CNC particles or CNC aggregates were separated from each other and had a size of less than 20 μm. Lambda-cyhalothrin was solubilized in the oil phase solvent and then added to the water and CNC composition. The resulting composition was homogenized using high-speed stirring (Turrax, 15,000 rpm, 2 times for 3 min) to obtain emulsified droplets with a size of 1-10 μm.

[0113] The composition was obtained in the same manner as described in Example 1. After reaching the desired droplet size, a crosslinking agent was slowly added with gentle stirring: citric acid (2 wt%), tannic acid (0.5 wt%) or glutaraldehyde (4 wt% of a 25% aqueous solution). After complete addition, the composition was heated to 60 ° C for 4 hours, then allowed to cool to room temperature. Example 3. Storage

[0114] An accelerated storage study was conducted on a CNC formulation with and without a glutaraldehyde-based crosslinker. Testing revealed clear improvements after storage at high temperatures and thermal cycling. The crosslinked sample showed no separation, while the non-crosslinked sample demonstrated degradation during thermal cycling. In addition, the pH and viscosity profiles were significantly less different from the initial measurements for the crosslinked sample, while a 2-unit drop in pH and significant thickening were observed for the sample without a crosslinker. A comparison of formulations (A) with 2% glutaraldehyde and (B) without glutaraldehyde are shown in Fig. 1 after 2 weeks of thermal cycling in a temperature range from -10 to 50°C every 20 hours. The results are presented in the table below. Example 4. Drying

[0115] Drying cross-linked and non-cross-linked samples on a glass slide allowed us to observe the fine structure of the emulsion upon evaporation of the aqueous carrier. Without a cross-linker, no fine structure was observed, and emulsion breakdown was evident. With the inclusion of glutaraldehyde- or citric acid-based cross-linkers, the fine structure could be visualized in detail using microscopy, demonstrating an increase in the mechanical strength of the CNC-based matrix at the interface. The microscopic images are shown in Fig. 2.

[0116] The composition was prepared in the same manner as described in Example 1 using the amounts indicated in the table above. Dimethyl phthalate (DMP) was loaded into the second phase. The composition was divided into three equal parts, with one batch left without crosslinking agent (instead of the crosslinking agent in the other samples, water was added to the total amount of 100% to maintain a constant loading), a citric acid-based crosslinking agent was added to the second batch, a glutaraldehyde-based crosslinking agent was added to the third batch, and all batches were cured at 50°C for 18 hours. Each sample was individually subjected to the following protocol to evaluate the diffusion of UV-active DMP through the matrix interfacial layer. 1) A 30 cm long piece of dialysis tubing was prepared by soaking in deionized water for 18 hours. 2) The lower end of the dialysis tubing was sealed by tying a knot.3) 1 mL of the formulation was injected into the center of the dialysis tubing and the top was tied. 4) The tubing was placed in 100 mL of deionized water in a 150 mL glass vial, shaken, and 3 mL was removed for the initial sample. 5) The glass vial containing the dialysis tubing was placed on a roller. 6) The UV spectrum of the 3 mL sample was recorded in the range of 250-300 nm on a UV spectrophotometer since DMP absorbs at 275 nm. 7) The absorbance at 275 nm was recorded. 8) The sample was returned to the glass vial containing the dialysis tubing. 9) The process was repeated after 30 minutes, 1 hour, 2 hours, or until a plateau was reached. The results of these studies are shown in Fig. 3. A release rate study showed that the use of a cross-linking agent reduces the rate of DMP release through the interfacial matrix compared to when no cross-linking agent is used. That is, in the absence of a cross-linking agent, a greater amount of DMP is released at a faster rate.

[0117] The composition was prepared in the same manner as described in Example 1 using the amounts indicated in the table above. The composition was divided into six equal parts, with Batch A left without a crosslinking agent. A citric acid-based crosslinking agent was added to Batches B and C at a loading of 4% w / w and 2% w / w, respectively. Tannic acid was added to Batches D and E at a loading of 2% w / w and 0.14% w / w, respectively. Glutaraldehyde was added to Batch F as a 25% aqueous solution (glutaraldehyde content 1% w / w, aqueous solution content 4%). All batches were cured at 50°C for 18 hours.Each sample was individually subjected to the following protocol, which is a slightly modified version of the International Cooperative Pesticide Analytical Council (CIPAC) Method MT 190 - Determination of CS Release Properties of Lambda-Cyhalothrin Formulations for assessing the diffusion of an agriculturally active ingredient through a matrix interfacial layer. This modification of the method excludes ethanol from the internal standard solution. 1. An internal standard (IS) solution was prepared containing dicyclohexyl phthalate (350 mg) dissolved in hexane (1 L). 2. Approximately 500 mg of the formulation was diluted in deionized water to 6 mL, and the exact weight of the applied formulation was noted. 3. 100 mL of the IS solution was added to the diluted formulation from step 2.4. The mixture was gently mixed, and a 1 mL aliquot of the hexane layer was removed and placed in the GC vial with 1 drop of trifluoroacetic acid. The vessel was then sealed and hermetically sealed.5.The sample was then placed on a horizontal roller, not upside down, and the rotation speed was set to 70 rpm.6. Additional 1-mL aliquots were removed from the hexane fraction and placed in the GC vessel at the desired time points of 5, 10, 15, 30, 60, 90, 180, 360, and 1440 minutes, with the addition of 1 drop of trifluoroacetic acid before sealing. The sample was returned to the roller after each aliquot removal.7. Lambda-cyhalothrin content was then measured by GC using the procedure described in CIPAC method MT190.

[0118] The results of these studies are shown in Fig. 4. The release rate study showed that the use of a cross-linking agent reduces the release rate of lambda-cyhalothrin through the interfacial matrix, depending on the type and amount of cross-linking agent used, compared to no cross-linking agent. Without a cross-linking agent, a pseudo-inverse exponential release curve was observed, with a release profile characterized by an initial burst that then tapers off over time. The use of citric acid ensures a stable and relatively rapid linear release of lambda-cyhalothrin, while glutaraldehyde and tannic acid provide a much more moderate release rate, with increasing amounts of tannic acid providing a slower release.

[0119] The formulation was prepared in the same manner as described in Example 1 using the amounts indicated in the table above. The release rate of these compositions was tested using the methodology from Example 6. The results are presented in Fig. 5, where a trend similar to that observed in Example 6 can be observed, where various crosslinkers weakened the release of lambda-cyhalothrin through the interfacial matrix. Tannic acid provided the highest barrier to release, followed by glutaraldehyde, then citric acid, which provided the weakest barrier to release of these crosslinkers. As a control, the absence of a crosslinker resulted in the highest release rate, illustrating the effect of crosslinkers on the diffusion of lambda-cyhalothrin.

[0120] After initial testing, the formulations were stored for two weeks at either 25°C or 54°C. The release rate was retested. The results are shown in Fig. 6. Generally, these cross-linked systems showed little change or slight improvement in release rate profiles and diffusion kinetics after storage, indicating their long-term physical stability as slow- or fast-release systems.

[0121] Although only a few illustrative embodiments of the present invention have been described in detail above, those skilled in the art will readily appreciate that numerous modifications to the illustrative embodiments are possible without substantially departing from the innovative ideas and advantages of the present invention. Accordingly, all such modifications are intended to be included within the scope of the present invention, as defined in the following claims.

Claims

1. A liquid pest control composition containing: first phase; the second phase, which is immiscible with the first phase and dispersed in it; a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and at least one agrochemically active ingredient in the second phase.

2. A liquid composition for regulating plant growth, containing: first phase; the second phase, which is immiscible with the first phase and dispersed in it; a matrix based on cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and at least one agrochemically active ingredient in the second phase.

3. The composition according to claim 1 or 2, wherein the cross-linked cellulose nanocrystals are cross-linked with glutaraldehyde.

4. The composition according to claim 1 or 2, wherein 40-80% of the interface surface between the first phase and the second phase is covered with cross-linked cellulose nanocrystals.

5. The composition of claim 1 or 2, wherein the first phase contains cellulose nanocrystals in an amount sufficient to change the viscosity of the composition by more than 10% compared to a composition that does not contain cellulose nanocrystals in the first phase.

6. The composition according to claim 1 or 2, wherein the cross-linked cellulose nanocrystals are cross-linked with citric acid.

7. The composition according to claim 1 or 2, wherein the cross-linked cellulose nanocrystals are cross-linked with tannic acid.

8. The composition according to claim 1 or 2, wherein the cross-linked cellulose nanocrystals are cross-linked with boric acid.

9. The composition according to claim 1 or 2, wherein the crosslinked cellulose nanocrystals constitute 0.1-5% w / w of the composition.

10. The composition according to claim 1 or 2, wherein the cross-linked cellulose nanocrystals are characterized by a multimodal distribution.

11. The composition according to claim 1 or 2, wherein the second phase comprises droplets with a median diameter of 1 to 10 microns.

12. The composition according to claim 1 or 2, wherein at least one agrochemically active ingredient is characterized by a slow release of the maximum payload through a matrix based on cross-linked cellulose nanocrystals.

13. The composition according to claim 1 or 2, wherein at least one agrochemically active ingredient is characterized by rapid release of the maximum payload through a matrix based on cross-linked cellulose nanocrystals.

14. A method for controlling the infestation of plant species by pests by diluting an effective amount of the concentrated composition according to claim 1 or 2 with an aqueous liquid carrier selected from water and a liquid fertilizer or a combination thereof, and applying the diluted composition to the plant species or their growing site.

15. A method for regulating plant growth by diluting an effective amount of a concentrated composition according to claim 1 or 2 with an aqueous liquid carrier selected from water and a liquid fertilizer or a combination thereof, and applying the diluted composition to a plant species or its growing site.

16. A method for producing a liquid composition according to any one of paragraphs 1-13, comprising: dissolving or suspending the agrochemically active ingredient in the second phase; incorporation of cellulose nanocrystals into the first phase, or the second phase, or both; combining the first phase and the second phase to form a composition; shaking the composition to form an emulsion; and ensuring the crosslinking of cellulose nanocrystals with the formation of a matrix shell around the droplets of the second phase.

17. The method of claim 16, further comprising including salt in the first phase and / or the second phase.

18. A plant seed coated with a composition according to any one of claims 1-13.

19. The seed according to claim 18, wherein the composition is dried.

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