Hydrolyzed protein dispersant

Abstract

The present invention relates to a dispersant for a suspending agent-based aqueous medium agrochemical formulation wherein the formulation comprises at least one dispersant which is a hydrolyzed plant protein having a molecular weight of at least 5,000 Da; and at least one agrochemical active agent. Preferably, the hydrolyzed protein is derived from potato, wheat or chickpea protein. The hydrolyzed protein may be chemically modified with a functional group selected from silicone or alkenyl succinic anhydride. The hydrolyzed protein may be cross-linked with an optionally alkoxylated di-or tri-glycidyl ether. The invention also relates to a method for providing dispersion in the agrochemical formulation with the hydrolyzed protein and a method for treating a crop plant with the formulation. Concentrates suitable for forming the formulations are also provided.

Description

[0001] The present invention relates to a dispersant for agrochemical formulations of the suspension concentrate type containing a hydrophobic solid agrochemical active ingredient, and a method for providing dispersion in said agrochemical formulations. The present invention also includes a method for treating crops with said formulations.

[0002] Agrochemical formulations generally include dissolved or dispersed components such as active ingredients and often additives or dispersants are added to the formulation to aid in the dispersion of these components.

[0003] The trend towards more water-based systems due to regulations has led to problems with less soluble (hydrophobic and slightly soluble) active ingredients. Additionally, the inclusion of more active ingredients in the formulation often leads to adverse crystal growth. A particular problem with agrochemical formulations is that it is becoming increasingly difficult to disperse the active ingredients, and this is particularly problematic due to the trend towards using poorly soluble or slightly soluble active ingredients.

[0004] There has also recently been a desire to remove fossil fuel-based components from agrochemical formulations and to provide more sustainable alternatives to traditional dispersants.

[0005] Therefore, there is a need to find dispersants that allow the formation of suspension concentrate type formulations with hydrophobic and slightly soluble active ingredients and that overcome the above problems. Additionally, the present invention aims to provide dispersants that have desirable properties such as dispersing hydrophobic solid active ingredients in suspension concentrate type formulations and that are from more sustainable sources. The present invention also aims to provide the use of agrochemical concentrates and diluted formulations containing said dispersants.

[0006] According to a first aspect of the present invention, there is provided an agrochemical formulation in an aqueous medium of the suspension concentrate type, comprising;

[0007] i) a hydrolyzed plant protein dispersant, said protein having a molecular weight of at least 5,000 Da; and

[0008] ii) at least one solid agrochemical active ingredient dispersed in an auxiliary aqueous medium.

[0009] According to a second aspect of the present invention, there is provided a concentrate formulation suitable for preparing the agrochemical formulation of the first aspect, said concentrate comprising;

[0010] i) a hydrolyzed plant protein dispersant, said protein having a molecular weight of at least 5,000 Da; and

[0011] ii) at least one solid agrochemical active ingredient dispersed in an auxiliary aqueous medium.

[0012] According to a third aspect of the present invention, there is provided the use of a hydrolyzed protein according to the first aspect as a dispersant in an agrochemical formulation containing a solid agrochemical active ingredient.

[0013] According to a fourth aspect of the present invention, there is provided a method of treating a plant to control pests and diseases, the method comprising applying the formulation of the first aspect and / or the diluted concentrate formulation of the second aspect to the plant or to the environment of the plant.

[0014] It has been found that hydrolyzed proteins provide desirable dispersion properties when used in agrochemical formulations of the suspension concentrate type having a hydrophobic solid agrochemical active ingredient. Additionally, hydrolyzed proteins can be obtained from sustainable, non-fossil fuel sources.

[0015] As used herein, the terms 'for example', 'for instance', 'e.g.' or 'including' are intended to introduce examples that further clarify the superordinate subject. Unless otherwise specified, these examples are provided solely to assist in understanding the applications described herein and are not intended to be limiting in any way.

[0016] It should be understood that when describing the number of carbon atoms in a substituent (e.g. 'C1-C6 alkyl'), the number refers to the total number of carbon atoms in that substituent, including the carbon atoms present in any branched groups. Additionally, when describing the number of carbon atoms in, for example, a fatty acid, this refers to the total number of carbon atoms including the carboxylic acid and any branched groups.

[0017] The term 'hydrolyzed protein' is used herein to refer to a protein that has been hydrolyzed. Hydrolyzed proteins can comprise protein fragments, polypeptides, peptides, amino acids and / or peptones.

[0018] The term 'hydrolyzed protein' is used herein to include polypeptides, peptides, amino acids and / or peptones. Polypeptides, peptides and amino acids can be prepared, for example, by acid, base and / or enzymatic hydrolysis of natural proteins. Base hydrolysis of proteins is preferred. In one embodiment, hydrolysis of potato proteins is preferred, especially those produced by base hydrolysis. The hydrolyzed protein component can also contain carbohydrates, for example hydrolyzed potato proteins can contain potato starch.

[0019] Hydrolyzed proteins can be produced by acid hydrolysis, base hydrolysis and / or enzymatic hydrolysis of preferably natural or renewable source proteins. Without being bound by theory, the advantage of base hydrolysis compared to acid or enzymatic hydrolysis is that base hydrolysis produces soluble hydrolyzed proteins of higher molecular weight compared to acid or enzymatic hydrolysis. Generally, acid hydrolysis can produce fragments with the smallest weight average molecular weight, base hydrolysis can produce the largest fragments, and enzymatic hydrolysis can produce fragments of intermediate size between acid and base hydrolysis.

[0020] The size of the fragments in hydrolyzed proteins is proportional to the number of amino acid residues in the fragments, since the fragments are derived from the long amino acid chains that make up the unhydrolyzed protein. Base hydrolysis can be advantageous in order to obtain hydrolyzed proteins of a desired molecular weight.

[0021] The amino compound for preparing the composition of the present invention may be a partially hydrolyzed protein. The term 'partially hydrolyzed protein' means a protein that is not completely hydrolyzed, that is, not hydrolyzed to the extent that only single amino acids remain in the amino compound.

[0022] The amino compound for preparing the composition of the present invention may be an unchemically modified hydrolyzed protein. The term 'unchemically modified hydrolyzed protein' means that the protein has not undergone other chemical modifications (or reactions) other than hydrolysis.

[0023] Preferably, the composition does not contain a protein component derived from an animal protein source. This is advantageous because the animal source may be undesirable to consumers. Preferably, the composition does not contain components derived from animals. Preferably, the composition is suitable for vegetarian consumers.

[0024] The hydrolyzed protein for use in the present invention is derived from a plant source or fermentation. Preferably a plant source. Examples of suitable proteins include collagen, chickpea, hemp, elastin, keratin, casein, wheat protein, wheat starch, potato protein, soy protein and / or silk protein. Particularly preferred are potato protein, hemp protein, and chickpea protein. Particularly preferred is potato protein.

[0025] The hydrolyzed protein can be formed from single amino acids or from amino acids contained in longer peptide chains derived from the hydrolyzed protein. Preferably, the hydrolyzed protein can be an amino acid chain formed by protein hydrolysis.

[0026] The dispersant may be a partially hydrolyzed protein, preferably obtained from a potato source, a wheat source, or a chickpea source.

[0027] The potato, wheat or chickpea protein source may be a potato, wheat or chickpea protein concentrate and / or isolate. As a first step, an aqueous dispersion of the potato, wheat or chickpea protein concentrate and / or isolate can be prepared, and as a second step, the protein can be hydrolyzed. The difference between the potato, wheat or chickpea protein source and the partially hydrolyzed protein may be that the partially hydrolyzed protein is more soluble in water at a reference temperature (e.g., room temperature) compared to the potato, wheat or chickpea protein source.

[0028] Partially hydrolyzed proteins can be produced by acid, base or enzymatic hydrolysis. Base hydrolysis is preferred. One or more enzymes can be used. Preferably, the enzymes are of microbial origin. The one or more enzymes can comprise carbohydrases and / or proteases. The hydrolysis can be carried out to the extent required to achieve the desired weight average molecular weight of the hydrolyzed protein. The degree of hydrolysis can be varied by changing the temperature, the acid / base / enzyme used and the time consumed. The resulting hydrolyzed protein can be filtered and / or treated to remove unwanted substances. For example, if acid hydrolysis is used, the hydrolyzed protein can be treated to remove any chloride anions present.

[0029] The molecular weight (weight average) of the protein component raw material (before hydrolysis) can vary over a wide range.

[0030] The weight average molecular weight (Mw) of hydrolyzed potato, wheat or chickpea proteins can be at least 5,000 Daltons (Da), preferably at least 8,000 Da, more preferably at least 10,000 Da, especially at least 15,000 Da. The weight average molecular weight can be at most 180,000 Da, preferably at most 160,000 Da, more preferably at most 140,000 Da, especially at most 130,000 Da, particularly at most 110,000 Da.

[0031] In the case where the hydrolyzed protein contains crosslinks, the molecular weight of the hydrolyzed protein before crosslinking can be lower. The lowest range of the weight average molecular weight (Mw) of hydrolyzed potato, wheat or chickpea proteins can be at least 3,000 Daltons (Da), preferably at least 4,000 Da.

[0032] The molecular weight will be determined by size exclusion chromatography, such as the size exclusion HPLC (SE-HPLC) described herein, especially the TSKgel GMPWXL protocol.

[0033] The hydrolysis will be carried out to the extent required to achieve the desired molecular weight and chain length of the hydrolyzed protein. The hydrolyzed protein can be filtered and treated to remove unwanted substances.

[0034] Preferably, the hydrolyzed protein component is capable of forming an aqueous solution.

[0035] Preferably, the amount of free amino acids in the hydrolyzed protein is less than 60% by weight. More preferably less than 55% by weight. It should be understood that since free amino acids have low solubility, it is desirable for their amount to be at a low level.

[0036] The dispersant can be a partially hydrolyzed protein derived from a hemp source. The hemp protein source can be hemp protein concentrate and / or isolate. As a first step, an aqueous dispersion of the hemp protein concentrate and / or isolate can be prepared, and as a second step, the protein can be hydrolyzed. The difference between the hemp protein source and the partially hydrolyzed protein can be that the partially hydrolyzed protein is more soluble in water at a reference temperature (e.g., room temperature) compared to the hemp protein source.

[0037] The partially hydrolyzed protein can be produced by acid, base, or enzymatic hydrolysis. Base hydrolysis is preferred. The hydrolysis can be carried out to the extent required to achieve the desired weight-average molecular weight of the hydrolyzed protein. The degree of hydrolysis can be changed by varying the temperature, the acid / base / enzyme used, and the time consumed. The resulting hydrolyzed protein can be filtered and / or treated to remove unwanted substances. For example, the hydrolyzed protein can be washed through a membrane to remove any salts present.

[0038] The molecular weight (weight-average) of the hydrolyzed hemp protein can vary over a wide range, e.g., from 1,000 Da to 500,000 Da, preferably from 5,000 Da to 200,000 Da, more preferably from 10,000 Da to 150,000 Da. In one embodiment, the hydrolyzed protein can have an average molecular weight in the range of 15,000 Da to 100,000 Da, preferably from 20,000 Da to 80,000 Da, especially from 25,000 Da to 75,000 Da, e.g., about 70,000 Da.

[0039] The molecular weight will be determined by size exclusion chromatography, such as the size exclusion HPLC (SE-HPLC) described herein.

[0040] The hydrolyzed protein can be copolymerized with a hydrophilic polymer. In particular, the hydrophilic polymer can be selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl alcohol copolymers, polyglycol alkyl acrylates, polyethers, polyether alkyl methacrylates, polyvinyl acetate, and polyvinyl acetate copolymers. Preferably, the hydrophilic polymer is selected from polyvinylpyrrolidone, polyethers, polyether alkyl methacrylates, and polyglycol alkyl acrylates.

[0041] More preferably, suitable hydrophilic polymers can be selected from polyvinylpyrrolidone, polyvinyl alcohol, polyglycol methacrylate (polyethylene glycol methacrylate) (HEMA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA). Most preferably, the hydrophilic polymer is polyvinylpyrrolidone.

[0042] The protein-hydrophilic polymer copolymer used in the present invention is suitably produced by reacting the protein with the hydrophilic polymer, preferably by free radical polymerization methods known in the art.

[0043] The ratio of the hydrophilic polymer to the protein (or the ratio of the hydrophilic polymer present in the copolymer to the protein) that react together to form the protein-hydrophilic polymer copolymer is suitably in the following ranges: 2 to 98:2 to 98%, preferably 5 to 70:30 to 95%, more preferably 10 to 50:50 to 90%, especially 15 to 40:60 to 85%, and particularly 20 to 25:75 to 80% by weight.

[0044] The resulting copolymer can be of any suitable type, including linear copolymers such as block copolymers or branched copolymers such as graft or star copolymers. Branched copolymers can be preferred. In particular, graft copolymers can be especially preferred.

[0045] The hydrophilic polymer used herein suitably has a molecular weight (weight average) in the range of 1,000 to 40,000, preferably 5,000 to 20,000.

[0046] Hydrolyzed chickpea protein can be preferred in the case of copolymerization with PVP and chemical modification with octenyl succinic anhydride (about 24% by weight).

[0047] The molecular weight (weight average) of the polymer binder described herein can be determined by the HPLC (SE-HPLC) described herein, especially the TSKgel GMPWXL protocol.

[0048] When present, the hydrophilic polymer can account for 10 to 50% by weight of the total copolymerization reagents. Preferably, 13% to 35% by weight of the reagents. More preferably, 15% to 30% by weight.

[0049] Chemically modified proteins and / or hydrolyzed proteins can also be used, for example, in the case where the protein has been covalently reacted with a functional group such as organosilicon or octenyl succinic anhydride. The hydrolyzed protein or each hydrolyzed protein can be independently further chemically modified, for example, in the case where the protein has been covalently reacted with the functional group.

[0050] One or more of the hydrolyzed proteins can be unchemically modified hydrolyzed proteins. The term 'unchemically modified hydrolyzed protein' means that the protein has not undergone further chemical modification (or reaction) other than hydrolysis.

[0051] The hydrolyzed polymer can be modified by more than one functional group. Alternatively, the hydrolyzed protein as a whole can comprise a mixture of proteins modified by different functional groups.

[0052] The modification can include reacting at least 20%, preferably more than 30%, more preferably more than 40% of the protein with the functional group.

[0053] In the presence, the modifying reagent can account for 6 to 30% by weight of the total comonomer. Preferably, 8% to 25% by weight of the reagent. More preferably, 10% to 20% by weight.

[0054] The hydrolyzed protein can contain crosslinks. The crosslinking agent can preferably be a di- or tri-glycidyl ether. The di- or tri-glycidyl ether can be optionally alkoxylated.

[0055] Suitable di-glycidyl ethers can be selected from bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, diglycidyl ether, diglycidyl resorcinol ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether. Preferably, selected from diglycidyl ether and neopentyl glycol diglycidyl ether.

[0056] Suitable tri-glycidyl ethers can be selected from castor oil glycidyl ether, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0057] In particular, in the case of selecting a crosslinking agent based on a content desired to be highly bio-based, a crosslinking agent selected from the following can be chosen: glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether, such as those available from Nagase ChemteX of Japan. Based on the total weight of the carbon-containing part of the composition, the bio-based carbon content can preferably be at least 70%, more preferably at least 80% bio-based.

[0058] The bio-based content level of the compound can be determined by using 14 the standardized analytical method ASTM D6866 for radiocarbon dating of C. ASTM D6866 distinguishes the carbon from bio-based inputs and the carbon from fossil-based inputs. With this standard, the percentage of carbon from renewable sources can be calculated from the total carbon of the sample.

[0059] The di- or tri-glycidyl ether can be alkoxylated. The alkoxylation of the di- or tri-glycidyl ether of the present invention includes using an alkylene oxide group, which is an oxyethylene unit (-CH2CH2-O-) and / or an oxypropylene unit (-CH2(CH3)CH2-O-).

[0060] Each alkylene oxide group can contain oxyethylene, oxypropylene, or a mixture of oxyethylene and oxypropylene units. In the case where the alkylene oxide chain contains both oxyethylene and oxypropylene, the alkylene oxide chain can be a block or random copolymer (forward or reverse) of oxyethylene and oxypropylene units.

[0061] The number of moles of ethylene oxide and propylene oxide present in each alkylene oxide group can independently be an integer from 2 to 20. For example, it should be understood that in the case where the value is 2, 2 moles of ethylene oxide and / or propylene oxide are present in that particular alkylene oxide chain.

[0062] The total number of moles of ethylene oxide or propylene oxide units present in each crosslinked molecule can be an integer value in the range from 2 to 20. Preferably, it ranges from 2 to 18. More preferably, it ranges from 4 to 14. Even more preferably, it ranges from 4 to 12. Most preferably, it ranges from 6 to 10. Thus, preferably in the range of 4 to 12 ethylene oxide units, and most preferably in the range of 6 to 10 ethylene oxide units, the alkylene oxide groups are formed.

[0063] When present, the crosslinking agent can account for 4 to 55% by weight of the total comonomer reagents. Preferably, 6% to 50% by weight of the reagents. More preferably, 8% to 40% by weight.

[0064] Specific preferred examples of alkoxylated di- and tri-glycidyl ethers can be selected from polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

[0065] In particular, polyethylene glycol (500) diglycidyl ether and polypropylene glycol (380) diglycidyl ether can be particularly preferred. It should be understood that 500 represents the number average molecular weight (M n n).

[0066] It is expected that crosslinking can be combined with copolymerization and / or chemical modification. Preferably, the crosslinked dispersant can be based on a hydrolyzed protein that is not chemically modified and is not a copolymer.

[0067] An additional advantage of crosslinking can be that the resulting dispersant can be biodegradable. The term 'biodegradable' is used herein to refer to a protein that has been degraded and hydrolyzed. The hydrolyzed protein can contain protein fragments, polypeptides, peptides, amino acids, and / or peptones.

[0068] The crosslinked hydrolyzed protein can be biodegradable. Preferably, at least 50% of the said dispersant degrades within a 28-day period, according to OECD methods 301B and 301F. More preferably, at least 60%. Most preferably, at least 70%.

[0069] Thus, compared to prior compounds used for this function, the crosslinked hydrolyzed protein can have the advantage of being more biodegradable and thus more sustainable.

[0070] The hydrolyzed proteins used herein without copolymerization or modification may suitably have a molecular weight (weight average) in the range preferably of 5,000 to 1,000,000, preferably 5,000 to 400,000, more preferably 12,000 to 300,000, particularly 15,000 to 280,000, and especially 17,000 to 260,000.

[0071] If copolymerized, the copolymers used herein may suitably have a molecular weight (weight average) in the range preferably of 10,000 to 400,000, more preferably 12,000 to 300,000, particularly 15,000 to 280,000, and especially 17,000 to 260,000.

[0072] If copolymerized and modified, the modified copolymers used herein may suitably have a molecular weight (weight average) in the range preferably of 1,000 to 40,000, preferably 10,000 to 120,000, more preferably 12,000 to 100,000, particularly 15,000 to 80,000, and especially 17,000 to 60,000.

[0073] If crosslinked, the crosslinked hydrolyzed proteins used herein may suitably have a molecular weight (weight average) in the range preferably of 5,000 to 800,000, preferably 5,000 to 400,000, more preferably 12,000 to 200,000, particularly 15,000 to 100,000, particularly 17,000 to 260,000, and especially 30,000 to 130,000.

[0074] The molecular weight (weight average) of the polymeric binders described herein can be determined by HPLC (SE-HPLC) described herein, particularly the TSKgel GMPWXL protocol.

[0075] The hydrolyzed proteins may contain other monomer units. In particular, monomers derived from the initiator used to prepare the hydrolyzed proteins in which copolymerization may be present.

[0076] The initiator may be selected from azo polymerization initiators or peroxide initiators. Azo polymerization initiators may be preferred. It should be understood that azo polymerization initiators are referred to as compounds having an azo group (R-N=N-R') that decompose by heat and / or light and form carbon radicals and are generally known in the polymerization field to have an initiator function.

[0077] Preferred peroxide initiators may be selected from tert-butyl peroxide and hydroperoxide.

[0078] Preferably, suitable azo initiators can be water-soluble and are selected from 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, or combinations thereof. Most preferably, the initiator can be 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V50).

[0079] When present, the initiator can be 3 to 20% by weight of the total comonomers. Preferably, 5% to 16% by weight of the reagent. More preferably, 7% to 12% by weight.

[0080] Preferably, the amino compound is derived from renewable sources. The amino compound is not derived from animal protein sources. This is advantageous because animal sources can be undesirable to consumers. Preferably, the composition does not contain animal-derived components. Preferably, the composition does not contain petrochemical-derived components.

[0081] Preferably, based on the total weight of the carbon-containing portion of the composition, the carbon-containing portion of the composition is at least 40% biobased, more preferably at least 50% biobased, especially at least 60% biobased (determined according to ASTM D6866).

[0082] The agrochemical active agent used in the formulations of the present invention is a solid agrochemical active agent. These are agrochemical active compounds in solid form, and this can include active agents that are relatively insoluble in water at room temperature and can thus also be hydrophobic.

[0083] In the present invention, hydrophobic solid agrochemicals mean those that are slightly soluble (less than 5% solubility at 20 °C to 25 °C) or practically insoluble in water.

[0084] In agrochemistry, the logarithm of the concentration ratio of an unionized solute in two solvents, namely octanol and water respectively, is used as the pesticide lipophilicity index and is called the octanol / water coefficient logP. The agrochemical active agent can have a logP value in the range of 0.1 to 5. More preferably, its range is 0.3 to 2.

[0085] The agrochemical active agent refers to a biocide, which in the context of the present invention is a plant protection agent, more particularly a chemical substance that can eliminate different forms of living organisms in various fields such as medicine, agriculture, forestry, and mosquito control. The so-called plant growth regulators are also included in the biocide category.

[0086] The biocides used in the agrochemical formulations of the present invention are generally divided into two subclasses:

[0087] Pesticides, including fungicides, herbicides, insecticides, algicides, molluscicides, acaricides and rodenticides, and

[0088] Antimicrobials, including bactericides, antibiotics, antibacterial agents, antiviral agents, antifungal agents, antiprotozoal agents and antiparasitic agents.

[0089] In particular, biocides selected from insecticides (insect-killing agents), fungicides or herbicides may be particularly preferred.

[0090] Fungicides that can be used in the examples of the present disclosure include, but are not limited to: (3-ethoxypropyl)-mercuric bromide, 2-methoxyethylmercuric chloride, 2-phenylphenol, 8-hydroxyquinoline, 8-phenylmercuryoxyquinoline, acibenzolar, acibenzolar-S-methyl, acypetacs, acypetacs-copper salt, acypetacs-zinc salt, aldimorph, allyl alcohol, ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin, bitertanol, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, binapacryl, benomyl, benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin S, Bordeaux mixture, boscalid, bromuconazole, ethirimol, Bordeaux mixture, buthiobate, butylamine, lime sulfur, captafol, captan, dimethomorph, decafentin, dehydroacetic acid, dichlofluanid, dichlone, dichlorophen, dichlozoline, dichlozoline-sodium salt, dichloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, fluopyram, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinitrobutyric acid esters, dinitrobutyric acid esters-4, dinitrobutyric acid esters-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, dichlofluanid, dithianon, dinitrophenol, dinitrophenol-ammonium salt, dinitrophenol-potassium salt, dinitrophenol-sodium salt, dodemorph,Dodemorph acetate, dodemorph benzoate, dodicin, dodicin-sodium salt, dodine, hydrazone bacterium ketone, edifenphos, epoxiconazole, etaconazole, thiram, thifluzamide, ethirimol, ethoxyquin, 2,3-dihydroxypropyl mercaptoethyl mercury, ethyl mercury acetate, ethyl mercury bromide, ethyl mercury chloride, ethyl mercury phosphate, thiabendazole, famoxadone, fenamidone, sodium thiram, iminoctadine, fenarimol, cyproconazole, furametpyr, fenhexamid, carboxin, fenpiclonil, fluopicolide, flumorph, fluopicolamine, fludioxonil, tricyclazole, fluquinconazole, flusilazole, sulfoxaflor, flutianil, flutolanil, prothioconazole, fluxapyroxad, captan, formaldehyde, ethyphos, fosetyl-aluminum, tridemorph, furmecyclox, furamorph, dimethirimol, furconazole, furconazole-cis, furfural, fenapanil, furafluconazole, guazatine, quinoline acrylate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiofos, merbromin, hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole, guazatine acetate, guazatine octanoate, iodomethane, ipconazole, iprobenfos, iprodione, valifenalate, isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, phthalide, mecarbinzid, pyrimethanil, fenpropidin, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-sodium, metam-potassium, metam-sodium, metazoxolon, metconazole, sulfosultap, furfural, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenolate, metiram, metominostrobin, metrafenone, thifluzamide, metiram, cyproconazole, methfuroxam, natamycin, nitrobenzene, phthalide, fluoromophenol, OCH, octhilinone, furfural, orysastrobin, oxadixyl, copper quinolate, oxpoconazole, oxpoconazole fumarate, oxycarboxin, pyribenzoxim, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, phenylmercury urea, phenylmercury acetate, phenylmercury chloride, catechol phenylmercury derivative,Phenylmercuric nitrate, phenylmercuric salicylate, chlorthiophos, tetrachorophthalide, picoxystrobin, propalis, ziram, polyoxin, polyoxorim, polyoxorim-zinc, potassium azide, potassium polysulfide, potassium thiocyanate, probenzazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propoxyquinoline, thiocarb, thiocarb hydrochloride, prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin, pyraoxystrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyriphenox, quinacetol, quinacetol sulfate, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane, silthiofam, silfluconazole, sodium azide, sodium o-phenylphenate, sodium pentachlorophenate, sodium polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin, tecloftalam, tecnazene, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thimerosal, thiophanate-methyl, thiram, thiazovivam, tioxymid, tolclofos-methyl, tolylmercury acetate, triadimefon, triadimenol, triazoxide, triarimol, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, dimethomorph, vinclozolin, cyanoxylanilide, zinc naphthenate, zineb, ziram, zoxamide and mixtures thereof.,

[0091] Insecticides that can be used in the examples of the present disclosure include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, amitraz, acetoprole, alphamethrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, neonicotinoids, athidathion, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, barban, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, bioresmethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromodichlorodiphenylmethane, bromophos, bromophos-ethyl, butacarb, buprofezin, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, lime sulfur, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorfenvinphos, chlorfenapyr, chlorthiophos, chlorpyrifos, chlorpyrifos-methyl, chlorpyrifos-ethyl, chlorprazophos, chlorpyrifos, cyromazine, cythioate, cyphenothrin, cismethrin, dimefox, dimethoate, dimethylvinphos, dioxathion, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene, dinocap, dinocap dicyclohexylamine, dinoprop, dinopenton, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, disulfoton, dithicrofos, d-limonene,Doramectin, ecdysterone, emamectin, emamectin benzoate, methiocarb, d-empenthrin, endosulfan, dioxathion, endrin, phoxim, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, ethofenprox, etrimfos, EXD, famphur, fenamiphos, amitraz, fenethacarb, fluphenoxuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flumethrin, fluvalinate, fonofos, formetanate, formetanate hydrochloride, butathiofos, fospirate, butocarboxim, fufenozide, furathiocarb, furethrin, beta-cyfluthrin, gamma-HCH, bifenazate, halofenozide, HCH, dieldrin, heptachlor, heptenophos, phosalone, flucycloxuron, aldrin, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, methyl iodide, formothion, chlorpyrifos-methyl, carbophenothion, isocarbophos, isofenphos-methyl, isoprocarb, isoprothiolane, isofenphos, oxydemeton-methyl, ivermectin, pyrethrins I, pyrethrins II, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, bromophos, lindane, lirimfos, lufenuron, fosthiazate, malathion, tebufenpyrad, mazidox, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, trichloroethane, dichloromethane, metofluthrin, propoxur, oxythioquinox, mevinphos, zectran, milbemectin, milbemycin oxime, sarin, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naphthalophos, naled, naphthalene, nicotine, hexaflumuron,Nitenpyram, nithiazine, phenothrin, flucycloxuron, lufenuron, omethoate, methiocarb, sulfotep, isosulfotep, disulfoton, p-dichlorobenzene, parathion, methyl parathion, novaluron, pentachlorophenol, permethrin, phenthoate, phenothrin, ethyl chlorthiofos, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, technical DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, cycloate, profluthrin, pyributicarb, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiophos, fosthiazate, protrifenbute, pymetrozine, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyrethrinate, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sulprofos, spinetoram, spinosad, spirodiclofen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, thiazopyr, TDE, tebufenozide, pyridaben, tebupirimfos, chlorfluazuron, tefluthrin, temephos, TEPP, transfluthrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetraflumethrin, lambda-cyhalothrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiosultap, thiosultap-sodium, thiodicarb, thiofanox, methylethyl disulfide, thiosultap, thiocyclam, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, trans-permethrin, tetradifon, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronate, trifenofos, triflumuron, trimethacarb, Z-73, vamidothion, vaniliprole, methiocarb, zeta-cypermethrin, zolaprofos and mixtures thereof.,

[0092] Herbicides that can be used in the examples of the present disclosure include, but are not limited to: chlorophenoxyacetic acid, 4-CPB, 4-CPP, 2,4-D, 3,4-DA, 2,4-dichlorophenoxybutyric acid, 3,4-DB, 2,4-DEB, bilanafos, 3,4-DP, barban, 2,4,5-T, 2,4,5-TBA, acetochlor, acifluorfen, acibenzolar, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, aziprotryne, barban, butafenacil, benazolin, bencarbazone, butralin, butroxydim, bensulfuron-methyl, bensulide, bentazone, benzadox, bipyrazon, benzipram, bicyclopyrone, pyrazolate, benzofluor, benzoylprop-ethyl, benthiocarb, bixlozone, bilanafos, bispyribac-sodium, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, buthiopyr, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chiorprocarb, carfentrazone, CDEA, CEPC, chlornitrofen, chlorthiamid, chlorthal-dimethyl, chlorbufam, chlorazifop, chlorazine, chlorbromuron, chlorthiophos, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron-ethyl, chlorobenzilate, chloropon, chlorotoluron, chloroxynil, chlorpropham, chlorsulfuron, chlorophthalim, chlorthiamid, cinidon-ethyl, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, cumyluron, cresol,Benzobromarone, cyanazine, cyanazine, cyclone, cyclosulfamuron, clethodim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cinmethylin, chloroxuron, dalapon, dazomet, isobutyl alachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, benzipram, 2,4-D propionic acid, quizalofop-P-tefuryl, diclofop, diclosulam, diethamquat, acetochlor, difenopenten, diuron, diquat, esprocarb, fluthiacet-methyl, diuron, DMPA, dinitrophenol, DSMA, EBEP, eglinazine, endothal, triazosulfuron, EPTC, erbon, ethalfluralin, ethametsulfuron-methyl, sulfosate, ethiozin, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, 2,4,5-T propionic acid, fenoxaprop-P-ethyl, quizalofop-P-ethyl, fenoxasulfone, fenteracol, benthiocarb, tecloftalam, fenuron, ferrous sulfate, flamprop-M, flamprop-M-isopropyl, flazasulfuron, florasulam, fluazifop-P-butyl, quizalofop-P-butyl, isopropyl flufenpyr-ethyl, flucarbazone-sodium, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron-methyl, fluridone, fluazifop-P, haloxyfop-P-methyl, hexachloroacetone, potassium hexafluoroarsenate, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane,iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, butamifos, hexazinone, isouron, isopolinate, prometryn, isoproturon, isoxuron, isoxaben, clomazone, isoxaflutole, oxadiargyl, tebutam, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPA-butanoate, MCPA-propionate, mecoprop-P, medinoterb, pretilachlor, flucetosulfuron, mesoprazine, mesosulfuron, mesotrione, metam, oxaziclomefone, bentazone, pyrazoleamide, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, metobenzuron, methiobencarb, methiozolin, methiuron, methometon, metribuzin, methyl bromide, methyl isothiocyanate, methyldymron, pyridafol, bromacil, metolachlor, sulfentrazone, methoxyphenone, quinclorac, molinate, monisouron, chloroacetic acid, linuron, diuron, paraquat dichloride, pebulate, napropamide, naproanilide, neburon, nicosulfuron, flufenacet, ethalfluralin, nitrofen, norflurazon, noruron, OCH, dimepiperate, o-dichlorobenzene, orthosulfamuron, oryzalin, propyzamide, oxadiazon, oxapyrazon, epoxysulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, metazachlor, cycloxydim, perfluidone, pethoxamid, phenmedipham, phenmedipham-ethyl, tebuthiuron, phenylmercuric acetate, aminopyralid, clopyralid, clodinafop-propargyl, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron-methyl, procyazine, profluazol, profluralin, prohydrojasmon, prometon, prometryn, propachlor, propanil, fenoxaprop-P-ethyl, propyrisulfuron, propyzamide, prosulfalin, prosulfuron, proxan, propaquizafop, pydanon, pyraclonil,Pyraflufen, pyrasulfotole, pyrazolate, pyrazosulfuron-ethyl, benzobicyclon, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyraclonil, pyribenzoxim, pyrimisulfan, pyrithiobac, pyroxasulfone, flazasulfuron, quinclorac, mefenpyr-diethyl, flumioxazin, pyraclonil, quinonamid, quizalofop-p-ethyl, quizalofop-P, rhodethanil, rimsulfuron, tembotrione, S-metolachlor, sebuthylazine, butralin, sethoxydim, cycluron, simazine, simeton, simetryn, sodium chloroacetate (SMA), sodium arsenite, sodium azide, sodium chlorate, mesotrione, ethofumesate, metosulam, sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, chloroxuron, trichloroacetic acid, propachlor, thidiazuron, tefuryltrione, tembotrione, pyraclonil, terbacil, terbutol, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron-methyl, thiobencarb, butylate, tioclorim, topramezone, tralkoxydim, triallate, ethoxysulfuron, triafamone, tribenuron-methyl, bentazone, triclopyr, cycloate, atrazine, trifloxysulfuron, trifluralin, flazasulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, triflusulfuron, vernolate, xylachlor, and mixtures thereof.

[0020] A safener means an active ingredient applied with a herbicide to protect crops from its injury. Some safeners that can be used in the present disclosure include, but are not limited to: benoxacor, thiobencarb, brassinolide, cloquintocet-mexyl, mefenpyr-diethyl, chloridazon, propyzamide, dicyclonon, piperophos, disulfoton, cloquintocet-ethyl, dichlormid, benoxacor, flurazole, oxabetrinil, isoxadifen-ethyl, pyrazolate, MG 191, MON 4660, phthalic anhydride (NA), dichlormid, R29148, N-phenylsulfonylbenzoic acid amide, and mixtures thereof.

[0093] Most preferably, the active agent present in the agrochemical formulation of the present invention can be selected from imidacloprid, flufenacet, azoxystrobin, or trifloxystrobin.

[0094] Agrochemical active compounds, including insecticides and fungicides, require formulations that allow the active compounds to be taken up by plants / target organisms.

[0095] The term 'agrochemical formulation' as used herein refers to a composition comprising an agrochemical active agent, and is intended to include all forms of the composition, including concentrates and spray formulations. Unless otherwise specified, the agrochemical formulations of the present invention may be in the form of concentrates, diluted concentrates or sprayable formulations.

[0096] The dispersants of the present invention can be combined with other components to form an agrochemical formulation comprising at least one agrochemical active agent.

[0097] The formulations of the present invention are formulations of the water-based suspension type. In the form of concentrates, these are generally used to disperse water-insoluble active ingredients, where the dispersion is either directly in the aqueous phase or absorbed in or adsorbed onto a solid carrier or as a microencapsulated active agent liquid or solution. These are generally referred to as suspension concentrates (SC), where the active compound is present as a solid.

[0098] Additionally, the formulations of the present invention can be suspoemulsions (SE), where two active ingredients with different physical properties are combined in one formulation. The suspoemulsion comprises a dispersion of insoluble solid active agents in water, where dispersed is a solution of a water-insoluble liquid or solid in oil.

[0099] Aqueous agrochemical concentrates are agrochemical compositions designed to be diluted with water (or a water-based liquid) to form the corresponding spray formulations.

[0100] Spray formulations are aqueous agrochemical formulations comprising all the components desired to be applied to plants or their environment. Spray formulations can be made by simple dilution of a concentrate containing the desired components (other than water).

[0101] Thus, the dispersant can be incorporated into formulations of agrochemical active compounds (in-can / built-in formulations).

[0102] Depending on user needs, the concentrates thus formed can contain generally up to 95% by weight of the agrochemical active agent. The concentrates can be diluted for use to obtain a diluted composition having an agrochemical active agent concentration of about 0.5% to about 1% by weight. In the said diluted composition (e.g., a spray formulation, where the spray application rate can be 10 to 500 l / ha -1 ), the agrochemical active agent concentration can be about 0.001% to about 1% by weight of the total spray formulation.

[0103] The dispersants of the present invention are generally used in amounts proportional to the amount of the active agrochemical in the formulation. In agrochemical formulation concentrates, the proportion of the dispersant depends on the solubility of the components in the liquid carrier. Generally, the concentration of the dispersant in the above-mentioned concentrates is 1% to 20% by weight. Preferably, 1.5% to 10% by weight. More preferably, 2% to 5% by weight.

[0104] The weight ratio of the dispersant to the agrochemical active ingredient in the concentrate and in the diluted concentrate agrochemical formulations is preferably from about 0.05:1 to about 0.2:1. More preferably, from about 0.7:1 to about 0.15:1. This ratio range is generally maintained for formulations in concentrate form (e.g., where adjuvants are included in a dispersible liquid concentrate or a dispersible solid granule formulation), and in spray formulations.

[0105] In cases where the concentrate (solid or liquid) serves as a source of the agrochemical active ingredient and / or the dispersant, the concentrate is generally diluted to form a spray formulation. The dilution can be carried out with water in a ratio of 1 to 10,000, especially 10 to 1,000 times the total weight of the concentrate to form a spray formulation.

[0106] In cases where the agrochemical active ingredient is present as solid particles in an aqueous end-use formulation, it is most commonly present as particles mainly containing the agrochemical active ingredient. However, if desired, the agrochemical active ingredient can be loaded onto a solid carrier such as silica or diatomaceous earth, which can be the solid carriers, fillers or diluent substances mentioned above.

[0107] Spray formulations generally have a pH ranging from moderately acidic (e.g., about 3) to moderately basic (e.g., about 10), and especially near-neutral pH (e.g., about 5 to 8). More concentrated formulations have a similar acid / alkalinity, but since they can be substantially non-aqueous, pH may not be an appropriate measure.

[0108] One problem with the presence of solid active ingredients is crystal growth during storage over a relatively short period of time, e.g., by "Ostwald ripening" of the active ingredient. Crystal growth by "Ostwald ripening" generally occurs in situations where smaller crystals (which have a larger surface area compared to larger crystals) dissolve in the aqueous phase and the substance is transported through the continuous phase to the nucleation sites of the larger crystals.

[0109] As a result, the crystals of the active ingredient can aggregate and precipitate, the formulation becomes non-uniform; during application, the filters and nozzles of the spray equipment can be blocked and the biological efficacy can be reduced. In aqueous thick suspensions, the purpose of the dispersant is to prevent excessive increase in crystal size.

[0110] It has also been found that the dispersant of the present invention has the effect of slowing down and / or stopping crystal growth in active ingredients having a tendency to grow crystals by "Ostwald ripening".

[0111] In particular, the dispersant combination is used for inhibiting crystal growth of active agents having particularly lipophilic properties - that is, hydrophobic and difficult-to-disperse active agents. In agrochemistry, the logarithm of the concentration ratio of an unionized solute in two solvents (n-octanol and water respectively) is used as the lipophilicity index of a pesticide and is called the octanol / water coefficient, i.e., Ko / w or logP. The polymers of the present invention allow for the preparation of aqueous agrochemical formulations containing at least one pesticide with a logP of -1.5 to +6 at 50 to 1100 g / L.

[0112] The formulation may also contain additional components selected from the following: pigments, dyes, micronutrients, agrochemical active agents, fillers, and combinations thereof.

[0113] Agrochemical formulations may include solvents (in addition to water) such as monopropylene glycol, oils, and first auxiliaries and co-auxiliaries associated therewith. The oil may be a vegetable oil or a mineral oil such as spray oil (including oils used as non-surfactant auxiliaries in spray formulations). The solvent may be included as a solvent for the auxiliaries and / or as a humectant, for example, especially propylene glycol. In use, the solvent is generally included in an amount of 5 wt% to 500 wt%, suitably 10 wt% to 100 wt% of the weight of the auxiliaries. The combination may also include salts such as ammonium chloride and / or sodium benzoate and / or urea, especially as gel inhibition auxiliaries.

[0114] Agrochemical formulations may also optionally include other components. These other components may be selected from those including the following:

[0115] Binders, especially binders that can be easily dissolved in water to provide a low-viscosity solution at a high binder concentration, such as polyvinylpyrrolidone; polyvinyl alcohol; carboxymethyl cellulose; gum arabic; sugars such as sucrose or sorbitol; starch; ethylene-vinyl acetate copolymers, sucrose, and alginates,

[0116] Diluents, absorbents, or carriers such as carbon black; talc; diatomaceous earth; kaolin; aluminum stearate, calcium stearate, or magnesium stearate; sodium tripolyphosphate; sodium tetraborate; sodium sulfate; sodium silicate, aluminum silicate, and mixed sodium-aluminum silicate salts; and sodium benzoate,

[0117] Disintegrants, such as surfactants, substances that swell in water, such as carboxymethyl cellulose, collodion, polyvinylpyrrolidone, and microcrystalline cellulose swelling agents; salts such as sodium acetate or potassium acetate, sodium carbonate, bicarbonate or sesquicarbonate, ammonium sulfate, and dipotassium hydrogen phosphate;

[0118] Wetting agents such as alcohol ethoxylates and alcohol ethoxylate / propoxylate wetting agents;

[0119] Dispersants such as sulfonated naphthalene formaldehyde condensates and acrylic copolymers such as comb copolymers having capped polyethylene glycol side chains on a polyacrylic acid backbone;

[0120] Emulsifiers such as alcohol ethoxylates, ABA block copolymers, or castor oil ethoxylates;

[0121] Defoamers such as polysiloxane defoamers, generally in an amount of 0.005% to 10% by weight of the formulation;

[0122] Viscosity regulators such as commercially available water-soluble or miscible gums, such as xanthan gum, and / or cellulosic materials, such as carboxymethyl, ethyl, or propyl cellulose; and / or

[0123] Preservatives and / or antimicrobial agents such as organic acids or their esters or salts such as ascorbic acid such as ascorbyl palmitate, sorbic acid such as potassium sorbate, benzoic acid such as benzoic acid and methyl and propyl 4-hydroxybenzoates, propionic acid such as sodium propionate, phenol such as sodium 2-phenylphenate; 1,2-benzisothiazolin-3-one; or formaldehyde itself or as paraformaldehyde; or inorganic materials such as sulfurous acid and its salts, generally in an amount of 0.01% to 1% by weight of the formulation.

[0124] The agrochemical formulation according to the invention may also contain components such as surfactant substances forming part of an emulsifier system. The surfactant may include surfactant dispersants.

[0125] Auxiliaries may be included in the compositions and formulations of the invention and used in the invention. Examples include alkyl polysaccharides (more properly called alkyl oligosaccharides); fatty amine ethoxylates such as coconut alkylamine 2EO; and derivatives of alk(en)yl succinic anhydrides, especially those described in PCT applications WO 94 / 00508 and WO 96 / 16930, or sorbitan as a derivative.

[0126] The formulation may contain at least one nutrient. Nutrients refer to chemical elements and compounds that are desirable or essential for promoting or improving plant growth.

[0127] Nutrients are generally described as macronutrients or micronutrients. Suitable nutrients for use in the concentrates of the invention are micronutrient compounds, preferably those that are solid or partially soluble at room temperature.

[0128] Micronutrients generally refer to trace metals or trace elements and are often applied at lower dosages. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum, and manganese. It is expected that the dispersants of the present invention will have broad applicability to all types of micronutrients.

[0129] Micronutrients can be in soluble form or included as insoluble solids and can be in the form of salts or chelates. Preferably, the micronutrients are in the form of carbonates or oxides.

[0130] Preferably, the micronutrients can be selected from zinc, calcium, molybdenum, or manganese, or magnesium. Particularly preferred micronutrients for use in the present invention can be selected from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0131] The amount of micronutrients in the concentrate is generally 5% to 40% by weight, more usually 10% to 35% by weight, especially 15% to 30% by weight, based on the total concentrate.

[0132] Generally, in the case of incorporation into the formulation during construction, the average particle size of the solid agrochemical is 50 μm to 100 μm, but generally the formulation is wet-milled after mixing to reduce the average particle size to 1 μm to 10 μm, more preferably 1 μm to 5 μm.

[0133] The formulations of the present invention can also contain at least one macronutrient. Macronutrients generally refer to those containing nitrogen, phosphorus, and potassium and include fertilizers such as ammonium sulfate, and water regulators. Suitable macronutrients include fertilizers and other nitrogen-containing compounds, phosphorus-containing compounds, or sulfur-containing compounds, and water conditioners.

[0134] Suitable fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium, or sulfur. Examples of such fertilizers include:

[0135] For nitrogen as a nutrient: nitrates and / or ammonium salts such as ammonium nitrate, including in combination with urea, e.g., as ureides, calcium ammonium nitrate, ammonium nitrate sulfate, ammonium phosphates, especially monoammonium phosphate, diammonium phosphate, and polyammonium phosphates, ammonium sulfate, and generally less commonly used calcium nitrate, sodium nitrate, potassium nitrate, and ammonium chloride;

[0136] For phosphorus as a nutrient: acidic forms of phosphorus such as phosphoric acid, pyrophosphoric acid, or polyphosphoric acid, but more commonly the salt forms such as ammonium phosphates, especially monoammonium phosphate, diammonium phosphate, and polyammonium phosphates, potassium phosphates, especially potassium dihydrogen phosphate, and potassium polyphosphates;

[0137] For sulfur as a nutrient: ammonium sulfate and potassium sulfate, e.g., potassium sulfate mixed with magnesium.

[0138] Biostimulants can enhance metabolic or physiological processes such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or combinations thereof. Non-limiting examples of biostimulants include seaweed extracts (such as Ascophyllum nodosum), humic acids (such as potassium humate), fulvic acids, inositol, glycine, and combinations thereof.

[0139] The invention also includes a method for treating plants with the formulation of the first aspect.

[0140] Accordingly, the invention also includes methods of use, including:

[0141] A method for eradicating or inhibiting plants by applying a spray formulation to the plant or the adjacent environment of the plant, such as the soil surrounding the plant, the spray formulation comprising at least one agrichemical in the dispersed phase and an adjuvant of the first aspect; and / or

[0142] A method for eradicating or inhibiting plant pests and diseases by applying a spray formulation to the plant or the adjacent environment of the plant, such as the soil surrounding the plant, the spray formulation comprising at least one agrichemical in the dispersed phase and an adjuvant of the first aspect, the agrichemical in the dispersed phase being one or more pesticides such as insecticides, fungicides or acaricides.

[0143] As used herein, the term 'dispersant' or 'disperse' refers to a compound which, when added to an agrichemical formulation, improves the desired effect of the agrichemical. The dispersant can affect the diluent, the mixture, the active ingredient or the target by improving the effect of the active ingredient.

[0144] Preferably, the dispersant of the invention can be used as the sole (dispersing) component or the main dispersing agent when directly formulated as a pesticide concentrate.

[0145] The substances of the invention are more easily diluted in agrichemical concentrates and develop a lower fluid viscosity in aqueous systems when in the concentrate or when diluted into water before spraying. This behavior provides improved ease of application in both the preparation and dilution of products containing them, especially when diluted in colder water. A reduction in foam stability has also been observed, which reduces the need for foam control agents. The dispersants of the invention can be added to agrichemical formulations without causing undesirable thickening or destabilization.

[0146] It should be recognized that the dispersion contains particles of solids with low water solubility and thus particle size and distribution are factors reflecting the stability of the dispersion.

[0147] It is important that there is a homogeneous distribution of the particles to ensure the stability of the dispersion over a longer period of time. Additionally, an effective dispersant ensures that the particles do not aggregate and cause phase separation. Thus, a dispersion with small particle size, homogeneous particle distribution, and limited growth of the particle size over time may be a more stable dispersion.

[0148] In terms of the form of the particle size distribution, the particles will have a median volume particle diameter value. It should be understood that the median volume particle diameter refers to the equivalent spherical diameter, which corresponds to the point on the distribution that precisely divides the distribution population into two equal halves. It is the point corresponding to 50% of the volume of all the particles, read on the cumulative distribution curve that relates the volume percentage to the particle diameter, i.e., 50% of the distribution is above this value and 50% of the distribution is below this value. This value is referred to as the "D(v,0.5)" value and is determined as described herein.

[0149] Additionally, it is also possible to refer to the "D(v,0.9)" values, and these values can be the equivalent spherical diameters corresponding to 90% of the volume of all the particles (read from the cumulative distribution curve relating the volume percentage - particle diameter), i.e., they are respectively the points where 10% of the distribution is above this value and 90% of the distribution is below this value.

[0150] The particle size values used to determine the D(v,0.5) and D(v,0.9) values are measured by the techniques and methods described in further detail herein. It should be understood that the particle size values defined below are based on a total of 2 - 3.5 wt% of the dispersant shown in the examples.

[0151] It is generally known that, in order to obtain a dispersion with desired properties, a particle size of 1 - 10 μm is preferred.

[0152] The particles present in the dispersant of the present invention can have an initial D(v,0.5) value on day 0 in the range of 2.5 μm to 8.0 μm. Preferably, the range is 3.0 μm to 7.0 μm. More preferably, the range is 3.2 μm to 6.0 μm. Most preferably, the range is 3.3 μm to 6.0 μm.

[0153] The particles present in the dispersant of the present invention can have a D(v,0.9) value on day 0 in the range of 5.0 μm to 14.0 μm. Preferably, the range is 5.5 μm to 12.0 μm. More preferably, the range is 6.0 μm to 11.0 μm.

[0154] The particles present in the dispersant of the present invention can have a D(v,0.5) value on day 7 at 54 °C in the range of 1.0 μm to 20.0 μm. Preferably, the range is 2.0 μm to 18.0 μm. More preferably, the range is 3.0 μm to 15.0 μm. Most preferably, the range is 3.5 μm to 13.0 μm.

[0155] The particles present in the dispersant of the present invention may have D(v, 0.9) values at 54 °C on the 7th day in the range of 5.0 μm to 75.0 μm. Preferably, the range is 6.0 μm to 65.0 μm. More preferably, the range is 7.0 μm to 62.0 μm. Most preferably, the range is 9.0 μm to 60.0 μm.

[0156] The particles present in the dispersion of the present invention maintain a change in either or both of D(v, 0.5) and D(v, 0.9) from day 0 to day 7 at 54 °C of not more than 150%, preferably not more than 130%, and most preferably not more than 110%.

[0157] The dispersion of the present invention thus provides good particle size and particle size distribution within the desired range of the dispersion concentrate. In addition, the suspension of the present invention maintains the desired particle size and particle size distribution over time during storage. That is, the particle size hardly decreases over time.

[0158] All the features described herein can be combined with any of the above aspects in any combination.

[0159] For a better understanding of the present invention, reference is now made, by way of example, to the following description.

[0160] It should be understood that all the tests and physical properties listed are determined at atmospheric pressure and room temperature (i.e., 25 °C), unless otherwise stated herein or unless otherwise stated in the test methods and procedures described. Examples

[0161] The following test methods were used to determine the effectiveness of the dispersant composition.

[0162] Particle size values - D(v0.5) and D(v0.9) values were determined by dynamic light scattering analysis using a Malvern Mastersizer 3000, equipped with a Hydro 3000SM accessory, run with deionized water, set at 2,500 rpm. The refractive index of the substance was set according to the following reference values, with an absorbance of 0.1, and 15,000 snapshots were taken within 15 seconds to obtain data. From the obtained particle size values, the D(v0.5) and D(v0.9) values were easily determined.

[0163] - Refractive index reference values: For imidacloprid - use a refractive index of 1.713, and for trifloxystrobin - use a refractive index of 1.511.

[0164] Stability - The stability of all formulations was evaluated after the specified time intervals at room temperature (RT, 25 °C) and 54 °C. Visual evaluation was performed on all samples to measure any possible sedimentation / creaming.

[0165] Suspendability - The sample is evaluated according to CIPAC MT 161. This method prepares a 250 ml aqueous dilution of the concentrated suspension agent mixed by inverting the graduated cylinder thirty times, allows it to stand in the graduated cylinder for a specified time (30 minutes) under defined conditions, and removes nine-tenths of the upper part. Then, chemical tests, gravimetric tests, or solvent extraction tests are performed on the remaining one-tenth. This method provides a stability index of the uniformity of the diluted concentrated suspension agent over time. Complete stability of the uniformity corresponds to 100%.

[0166] pH - Measured as a concentrate formulation according to CIPAC MT 75.

[0167] Weight-average molecular weight - Determined by size exclusion high performance liquid chromatography (SE-HPLC). The HPLC equipment and settings used are described below.

[0168] HPLC (SE-HPLC) equipment and settings - TSKgel GMPWXL protocol

[0169]

[0170] Synthesis methods for producing substances:

[0171] ● Method for hydrolyzing potato protein (C7)

[0172] Disperse the potato protein isolate powder in water. Add peracetic acid to the slurry and stir the slurry for 24 hours. Remove peracetic acid from the solution by repeated precipitation washing with fresh water. Then raise the acid-treated potato slurry to pH > 12.5 with NaOH (25%). Then stir the slurry for 24 hours, subsequently lower the pH to 9.0 and remove any undissolved substances. Then precipitate the soluble protein at pH 4 and wash the precipitate with fresh water. After washing, dissolve the precipitate by raising the pH to 6 with NaOH (25%). Then preserve the solution to prevent microbial growth.

[0173] ● Method for potato protein (C1)

[0174] Mix potato protein (400 g) into water (2800 g) and heat to 40 °C. Add NaOH (25%, 250 g) and stir and react at the temperature for 22 hours. Add hydrogen peroxide (35%, 34.5 g) and stir and react for 45 minutes, then repeat the peroxide addition. Stir and react for 1 hour 15, then turn off the heating and add HCl (28%) to lower the pH to 9.5. Filter the reaction to remove any insoluble substances. Adjust the substance to pH 4.0 with HCl (28%) to precipitate the protein. Add water to raise the reaction volume to 5000 ml. Let the protein precipitate overnight, then remove the water and redissolve the solid by raising the pH to 6.0 with NaOH (25%). Preserve the final product and then filter.

[0175] Mix hydrolyzed potato protein (250 g) with vinyl pyrrolidone (15.0 g) and heat to 85 °C. In another 50 mL beaker, add 4,4'-azobis(4-cyanovaleric acid) (5.0 g) to 25 ml of distilled water. Slowly stir and add NaOH (25%) to raise the pH of the initiator solution to 6.0 to dissolve the powder. After dissolution, add the initiator solution to the reaction within 3 hours. After completion of the initiator addition, stir and react the reaction for another 3 hours at the temperature. Let the reaction cool, then filter.

[0176] Method for potato protein / polyvinyl pyrrolidone (C2)

[0177] Alkaline hydrolysis product preparation - Add potato protein isolate (100 g) and water (500 g) to a 1-liter beaker. Mix the slurry and heat to 40 °C. Add NaOH (25%, 75 g) to the slurry, cover the reaction and stir for 22 hours. Then add hydrogen peroxide (35%, 6 g) and add more hydrogen peroxide (35%, 6 g) after 1 hour. Stir the reaction for 1 hour, then add HCl (28%) to lower the pH to 10. Centrifuge to remove the insoluble substances and add more HCl (28%) to precipitate the protein at pH 4.0. Wash the precipitate with fresh water, then redissolve by raising the pH to 6.2 with NaOH (25%). Preserve the protein solution to prevent microbial growth.

[0178] For copolymerization with vinylpyrrolidone - A solution of hydrolyzed protein (above) (200.2 g) and vinylpyrrolidone (13.65 g) was added to a 400 ml beaker. The solution was stirred with a magnetic stirrer and heated to 75 °C. Over 3 hours, an aqueous (25 g) solution of V-50 initiator, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (5.44 g) was added to the above protein / monomer solution. After the addition was complete, the line was rinsed with water (10 g). The reaction was covered and stirred for an additional 3 hours at temperature, then allowed to cool to room temperature. After cooling, the solution was filtered to remove any precipitate.

[0179] All protein PVP samples were prepared in the same manner, but varying the concentrations of monomer and initiator.

[0180] ● Method for copolymers of potato protein (C3)

[0181] To prepare the alkali protein hydrolysate - Potato protein (200 g) was mixed into water (1400 g) and heated to 50 °C. NaOH (25%, 125 g) was added. The slurry was stirred at temperature for 6 hours, then heating was turned off and hydrogen peroxide (16.5 g) was added. After 20 minutes, HCl (28%) was added to lower the pH to 10 and the peroxide addition was repeated. Then the slurry was filtered to remove any insoluble material.

[0182] To modify with OSA - A batch of hydrolyzed protein (854 g) was heated to 40 °C and N-octenyl succinic anhydride (10 g) was added. The pH was maintained at 10.0 to 10.5 for 6 hours, then HCl (28%) was added to lower the pH to 4. The solids were allowed to precipitate overnight. The aqueous layer was removed and additional water was added to bring the volume of the material to 400 ml. The pH was raised to 6.5 with NaOH (25%) to redissolve the solid material. The final product was preserved and filtered.

[0183] To prepare the VP copolymer - The modified potato protein (200 g) was mixed with vinylpyrrolidone (14.3 g) and heated to 85 °C. An aqueous (35 g) solution of 4,4'-azobis(4-cyanovaleric acid) (5.7 g) adjusted to pH 6.5 was added to the reaction over 3 hours. Then the reaction was allowed to react for an additional 3 hours, then allowed to cool.

[0184] Method for copolymers of chickpea protein (C4)

[0185] Alkaline Hydrolysis Product Preparation - In a 2 L beaker, stir chickpea protein isolate (200 g) into water (1000 g). Heat the slurry to 45 °C and add NaOH (25%, 150 g). Cover the reaction and stir for 21 h. Add HCl (28%) to lower the pH to 10 and filter the slurry to remove any insoluble material. Then add HCl (28%) to precipitate the protein at pH 4.0. Wash the precipitate with fresh water and then redissolve the solid by raising the pH to 10.2 with NaOH (25%).

[0186] For Modification with OSA - Add a solution of hydrolyzed protein (above) (300 g) to a 600 ml beaker and heat the solution to 40 °C. Raise the pH of the solution to pH 10.2 with NaOH (25%). Add N-octenyl succinic anhydride (15.0 g) over 30 min. Maintain the pH at 10.0 to 10.2 throughout the addition and for 4 h thereafter. After this time, add HCl (28%) to lower the pH to 6.5. Stir the product overnight to dissolve any precipitate formed during the pH adjustment.

[0187] For Copolymerization with Vinylpyrrolidone - Add a solution of the above-modified hydrolyzed protein (200 g) and vinylpyrrolidone (10.0 g) to a 400 ml beaker. Stir the solution with a magnetic stirrer and heat to 75 °C. Add a further aqueous (20 g) solution of the V-50 initiator, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (4.0 g), to the protein / monomer solution over 3 h. After the addition is complete, rinse the line with water (10 g). Cover the reaction and stir at temperature for a further 3 h, then allow to cool to room temperature. After this cooling, filter the solution to remove any precipitate.

[0188] ● Method for Copolymers of Hemp Proteins (C5)

[0189] Alkaline Hydrolysis Product Preparation - To a 1 L beaker, mix hemp protein isolate (150 g) and water (600 g). Heat the slurry to 45 °C and add NaOH (25%, 95 g). Cover the slurry and stir at temperature for 21 h. Then add HCl (28%) to lower the reaction pH to 10.0. Then centrifuge the slurry to remove any insoluble material and subsequently precipitate at pH 4.0 by adding HCl (28%). Wash the precipitate with fresh water and then redissolve at pH 6 by adding NaOH (25%). Then preserve the hydrolyzed protein to prevent microbial growth.

[0190] Vinyl pyrrolidone copolymerization - Add a solution of the above - modified hydrolyzed protein (100 g) and vinyl pyrrolidone (5.0 g) to a 250 - ml beaker. Stir the solution with a magnetic stirrer and heat to 75 °C. Add a solution of V - 50 initiator, 2,2'-azobis(2 - methylpropionamidine) dihydrochloride (2.0 g) in water (15 g) to the protein / monomer solution over 3 hours. After the addition is complete, rinse the line with water (5 g). Cover the reaction and stir for an additional 3 hours at temperature, then allow it to cool to room temperature. After cooling, filter the solution to remove any precipitate.

[0191] ● Method for quaternizing potato protein (C6)

[0192] Add hydrolyzed protein (C8) (400 g) to a 600 - ml beaker and adjust the pH to 10.2 with NaOH (25%). Heat the solution to 40 °C and add 2,3 - epoxypropyltrimethylammonium chloride (70%, 9.0 g). Maintain the reaction pH with NaOH (25%) for 4 hours, then add HCl (28%) to lower the pH to 6.5.

[0193] ● Method for cross - linking wheat protein with PEG500DGE (C8)

[0194] Mix wheat protein (400 g) into water (1600 g) and heat to 40 °C. Add NaOH (25%, 248 g) and stir the reaction for 20 hours. Add hydrogen peroxide (22.5 g) and stir the reaction for 1 hour, then repeat the peroxide addition. Add HCl (28%) to lower the solution pH to 10.5. Filter the hydrolysis product to remove insolubles, then evaporate and concentrate.

[0195] For cross - linking, heat the hydrolyzed wheat protein (20.6% active agent, 300 g) to 60 °C. Add PEG500DGE (6 g) to the reaction and after 30 minutes, add more PEG500DGE (3 g) and maintain the reaction at 10.0 - 10.4 for 6 hours. Add HCl (28%) to lower the pH to 6.0 and preserve.

[0196] ● Method for cross - linking potato protein with PEG500DGE (C9)

[0197] Stir potato protein (100 g) into water (700 g) and heat to 60 °C. Add NaOH (25%, 65 g). Stir the high pH reaction for 6 hours, then add HCl (28%) to lower the pH to 11.0. Turn off the heat and add hydrogen peroxide (8.6 g). Repeat the peroxide addition after 30 minutes. Filter the material to remove any insolubles. Then heat the turbid solution to 60 °C and add PEG500DGE (10 g). Maintain the pH at 10.0 - 10.4 with NaOH (25%). After 1 hour, repeat the PEGDGE addition and stir the reaction at temperature for 24 hours. After 24 hours, lower the pH to 5.5 and evaporate the final material to RI 30 and perform preservation.

[0198] ● Method for wheat protein cross-linked with NPDGE (C10)

[0199] Mix potato protein (400 g) into water (2800 g) and heat to 40 °C. Add NaOH (25%, 250 g) and stir at temperature for 22 hours. Add hydrogen peroxide (35%, 34.5 g) and stir the reaction for 45 minutes, then repeat the peroxide addition. Stir the reaction for 1 hour 15, then turn off the heat and add HCl (28%) to lower the pH to 9.5. Filter the reaction to remove any insoluble material. Heat a batch of this material (600 g) to 60 °C and adjust to pH 10.5. Add NPDGE (6.5 g) and after 1 hour add an additional amount of NPDGE (6.5 g). Then stir the reaction at 40 °C for 18 hours. Then lower the reaction pH to 4.0 with HCl (28%) to precipitate the cross-linked protein. Remove the aqueous layer and redissolve the solid by raising the pH to >6. Perform preservation on the final product.

[0200] ● Method for potato protein cross-linked with NPDGE (C11)

[0201] Alkaline protein hydrolysate - Mix potato protein (400 g) into water (2800 g) and heat to 40 °C. Add NaOH (25%, 250 g) and stir at temperature for 22 hours. Add hydrogen peroxide (35%, 34.5 g) and stir the reaction for 45 minutes, then repeat the peroxide addition. Stir the reaction for 1 hour 15, then turn off the heat and add HCl (28%) to lower the pH to 9.5. Filter the reaction to remove any insoluble material. Adjust the material to pH 4.0 with HCl (28%) to precipitate the protein. Add water to raise the reaction volume to 5000 ml. Let the protein precipitate overnight, then remove the water and redissolve the solid by raising the pH to 6.0 with NaOH (25%). Then perform preservation on the reaction.

[0202] Crosslinking - Heat hydrolyzed potato protein (150 g) to 60 °C and adjust to pH 10.2. Add NPDGE (1.5 g) and stir the reaction at the temperature while controlling the pH for 24 hours. Then precipitate the product at pH 4 with HCl (28%). Remove the aqueous layer and redissolve the solid at pH 6 and perform preservation.

[0203] ● Method for wheat protein crosslinked with NPDGE (C12)

[0204] Mix wheat protein (100 g) into water (700 g) and heat to 40 °C. Add NaOH (25%) (65 g) and stir the reaction for 18 hours. Remove any insoluble matter via filtration, adjust the pH to pH 10.2, heat to 60 °C and add NPDGE (20 g). Stir the reaction for 18 hours, then precipitate at pH 2.0. Recover the solid, redissolve at pH 6.0 and perform preservation.

[0205] - Method for potato protein crosslinked with BDGE (C13)

[0206] Mix potato protein (200 g) into water (1400 g) and heat to 50 °C. Add NaOH (25%, 125 g). Stir the slurry at the temperature for 6 hours, then turn off the heat and add hydrogen peroxide (35%, 16.5 g). After 20 minutes, add HCl (28%) to lower the pH to 10 and repeat the peroxide addition. Then filter the slurry to remove any insoluble matter. Heat a portion of the hydrolyzed protein (860 g) to 60 °C and add BDGE (10 g). After 1 hour, repeat the addition of BDGE (10 g) and stir the reaction for 6 hours. Keep the pH at 10.0 to 10.5 all the time. Lower the solution pH to 4.0 to precipitate the protein. Remove the aqueous layer, redissolve the solid layer by raising the pH to 6.4 with NaOH (25%) and perform preservation.

[0207] The substances produced

[0208] By the methods detailed above, the following hydrolyzed proteins are produced for testing:

[0209] ● C1 - Copolymer of potato protein / polyvinylpyrrolidone, molecular weight about 196,000 daltons, activity about 16%

[0210] ● C2 - Copolymer of potato protein / polyvinylpyrrolidone, molecular weight about 18,000 daltons, activity about 17.5%

[0211] ● C3 - Copolymer of potato protein / octyl succinic anhydride polyvinylpyrrolidone, molecular weight about 43,000 Daltons, activity about 21%

[0212] ● C4 - Copolymer of chickpea protein / octyl succinic anhydride polyvinylpyrrolidone, molecular weight about 38,000 Daltons, activity about 24%

[0213] ● C5 - Copolymer of hemp protein / polyvinylpyrrolidone, molecular weight about 159,000 Daltons, activity about 22%

[0214] ● C6 - Quaternized potato protein, molecular weight about 10,200 Daltons, activity about 14%

[0215] ● C7 - Hydrolyzed potato protein, molecular weight about 71,000 Daltons, activity about 11%

[0216] ● C8 - Wheat protein crosslinked with PEG500DGE, molecular weight about 50,850 Daltons, activity about 21.3%

[0217] ● C9 - Potato protein crosslinked with PEG500DGE, molecular weight about 21,095 Daltons, activity about 20.8%

[0218] ● C10 - Potato protein crosslinked with NPDGE, molecular weight about 90,128 Daltons, activity about 14.19%

[0219] ● C11 - Potato protein crosslinked with NPDGE, molecular weight about 52,294 Daltons, activity about 20.45%

[0220] ● C12 - Wheat protein crosslinked with NPDGE, molecular weight about 34,832 Daltons, activity about 16%

[0221] ● C13 - Potato protein crosslinked with BDGE, molecular weight about 77,000 Daltons, activity about 19%

[0222] NPDGE - Neopentyl glycol diglycidyl ether.

[0223] PEG500DGE - Polyethylene glycol (500) diglycidyl ether.

[0224] BDGE - Butanediol diglycidyl ether

[0225] VP - N - Vinylpyrrolidone

[0226] Test using imidacloprid

[0227] Prepare a 550 g / L imidacloprid suspension concentrate (SC) using the copolymer formed above according to Table 1 below, with low levels of dispersant and wetting agent. Xanthan gum (commonly used for structuring) is omitted.

[0228] Table 1 - 550 g / L Imidacloprid Formulation

[0229]

[0230] Test with Trifloxystrobin

[0231] Prepare a 500 g / L trifloxystrobin SC using the copolymer formed above according to Table 2 below, with low levels of dispersant and wetting agent. Xanthan gum (commonly used for structuring) is omitted.

[0232] Table 2 - 500 g / L Trifloxystrobin Formulation

[0233] Component Function g / 100mL % w / w Trifloxystrobin Fungicide 51.02 44.46 C3 / C5 / C6 Dispersant 2.50 2.18 Atlas G-5004LD Wetting agent 2.50 2.18 Silcolapse 5020 Defoamer 0.20 0.17 Proxel GXL Biocide 0.10 0.09 Pricerine 9091 Antifreeze 6.00 5.23 Water Aqueous phase 52.42 45.69

[0234] Test with Diflufenican

[0235] Prepare a 500 g / L diflufenican SC using the dispersant formed above according to Table 3 below, with low levels of dispersant and wetting agent. Xanthan gum (commonly used for structuring) is omitted.

[0236] Table 3 - 500 g / L Diflufenican Formulation

[0237] Component Function g / 100mL % w / w Diflufenican Fungicide 51.02 44.46 C1 / C9 / C12 Dispersant 2.50 2.18 Atlas G-5004LD Wetting agent 2.50 2.18 Silcolapse 5020 Defoamer 0.20 0.17 Proxel GXL Biocide 0.10 0.09 Pricerine 9091 Antifreeze 6.00 5.23 Water Aqueous phase 52.42 45.69

[0238] Results

[0239] Then, test the formulations (imidacloprid, trifloxystrobin, and diflufenican) at room temperature (RT) and 54 °C for 7 days according to the test plan shown in Table 3 below:

[0240] Table 4 - Test Plan

[0241]

[0242] The results obtained are shown in Tables 5 to 8 below.

[0243] Table 5 - Results of Imidacloprid Formulations for C1, C2, C4, C7, C8

[0244]

[0245] Table 6 - Results of Imidacloprid Formulations for C9 to C13

[0246]

[0247] Table 7 - Results of Trifloxystrobin Formulations for C3, C5, and C6

[0248]

[0249] Table 8 - Results of fomesafen formulations of C1, C9, and C12

[0250]

[0251] Biodegradation

[0252] The biodegradation of the test samples was provided with results referring to the OECD standards noted in Table 9.

[0253] Table 9 - Classification of biodegradability

[0254]

[0255] The results obtained are shown in Table 10.

[0256] Table 10 - Biodegradability results of C1, C4, C10, and C12

[0257] Sample Test method Result C1 OECD 301B Readily biodegradable C4 OECD 301B Readily biodegradable C10 OECD 301B Readily biodegradable C12 OECD 301B Readily biodegradable

[0258] All the samples tested showed a high level of biodegradability.

[0259] Each protein showed excellent efficacy regarding suspendability and storage stability. The particle size efficacy showed good control within 7 days, anti - flocculation, growth limitation, and D(0.9) less than 10 microns. Additionally, good rheological efficacy was also observed.

[0260] It should be understood that the present invention is not limited to the details of the above - described embodiments, which are merely exemplary descriptions. Many variations are possible.

Claims

1. Aqueous medium agrochemical formulation of the suspension concentrate type, comprising: i) a hydrolyzed plant protein dispersant, said protein having a molecular weight of at least 5,000 Da; and ii) at least one solid agrochemical active ingredient dispersed in an auxiliary aqueous medium.

2. The formulation according to claim 1, wherein the hydrolyzed protein is derived from potato protein, hemp protein, and chickpea protein.

3. The formulation according to claim 2, wherein the weight-average molecular weight (Mw) of the hydrolyzed potato, wheat, or chickpea protein ranges from 8,000 Da to 130,000 Da.

4. The formulation according to any one of the preceding claims, wherein the hydrolyzed protein is derived from potato protein.

5. The formulation according to any one of the preceding claims, wherein the hydrolyzed protein is copolymerized with a hydrophilic polymer selected from the following: polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl alcohol copolymer, polyglycol alkyl acrylate, polyether, polyether alkyl methacrylate, polyvinyl acetate, and polyvinyl acetate copolymer.

6. The formulation according to claim 5, wherein the hydrophilic polymer is selected from polyvinylpyrrolidone, polyvinyl alcohol, polyglycol methacrylate (HEMA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA).

7. The formulation according to any one of the preceding claims, wherein the hydrolyzed protein is chemically modified by covalent reaction with a functional group selected from organosilicon or alkenyl succinic anhydride.

8. The formulation according to any one of the preceding claims, wherein the hydrolyzed protein contains crosslinks, and the crosslinking agent is an optionally alkoxylated di- or tri-glycidyl ether.

9. The formulation according to claim 8, wherein the crosslinking agent is selected from bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, diglycidyl ether, diglycidyl resorcinol ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, castor oil glycidyl ether, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether.

10. The formulation according to claim 8 or claim 9, wherein the crosslinking agent is selected from glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.

11. The formulation according to any one of claims 8 to 10, wherein the crosslinked hydrolyzed protein has a molecular weight (weight-average) in the range of 12,000 to 200,000.

12. A concentrate formulation suitable for preparing an agrochemical formulation according to any one of claims 1 to 10, said concentrate comprising: i) a hydrolyzed plant protein dispersant, said protein having a molecular weight of at least 5,000 Da; and ii) at least one solid agrochemical active ingredient dispersed in an auxiliary aqueous medium.

13. The concentrate formulation according to claim 12, wherein the formulation is a thick suspension concentrate (SC) or a suspension emulsion (SE).

14. Use of the hydrolyzed protein according to claim 1 as a dispersant in an agrochemical formulation comprising a solid agrochemical active ingredient.

15. A method of treating plants to control pests and diseases, the method comprising applying the formulation according to any one of claims 1 to 11 and / or a diluted concentrate formulation according to any one of claims 12 to 13 to the plants or to the surrounding environment of the plants.

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