Dispersant for hydrolyzed proteins

Abstract

The present invention relates to a dispersant for a suspension-type water-borne pesticide formulation, the formulation comprising at least one dispersant that is a hydrolyzed vegetable protein having a molecular weight of at least 5,000 Da and at least one pesticide active. 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 optionally be crosslinked with an alkoxylated diglycidyl ether or triglycidyl ether. Also provided are methods for using the hydrolyzed protein to provide dispersibility in the pesticide formulation and methods for treating crops with such formulations. Concentrates suitable for forming the formulations are also provided.

Description

[Technical Field]

[0001] The present invention relates to dispersants for suspension-type pesticide formulations containing hydrophobic solid pesticidal active materials, and methods of providing dispersibility in such pesticide formulations. The present invention also includes methods of treating crops with such formulations.

[0002] Pesticide formulations typically contain dissolved or dispersed ingredients, such as the active substance, and additives or dispersants are often added to the formulation to aid in the dispersion of these ingredients.

[0003] Regulations are driving a move towards water-based systems, but problems arise with active substances that are not very water-soluble (hydrophobic and poorly soluble). Furthermore, in many cases, the inclusion of more active substance in the formulation can lead to undesirable crystal growth. A particular problem with pesticide formulations is the increasing difficulty of dispersing the active substance, which is particularly problematic with the trend towards using poorly or poorly soluble active substances.

[0004] In recent years, there has also been a desire to remove fossil fuel-based components from pesticide formulations and provide more sustainable alternatives to traditional dispersants.

[0005] Therefore, there is a need to find a dispersant that allows the formation of a suspension containing a hydrophobic, poorly soluble active substance and overcomes the above-mentioned problems. Furthermore, the present invention aims to provide a dispersant that has desirable properties, such as the dispersibility of a hydrophobic solid active substance in a suspension formulation, and that is derived from more sustainable sources. The present invention also aims to provide uses of pesticide concentrates and dilution formulations containing the dispersant.

[0006] According to a first aspect of the present invention, there is provided an aqueous suspension-type pesticide formulation, i) a dispersant of hydrolyzed vegetable protein having a molecular weight of at least 5,000 Da; and ii) at least one solid pesticidal active material dispersed in said aqueous medium; The present invention provides a suspension-type water-borne pesticide formulation comprising:

[0007] According to a second aspect of the present invention there is provided a concentrate formulation suitable for making an agrochemical formulation of the first aspect, the concentrate comprising: i) a dispersant of hydrolyzed vegetable protein having a molecular weight of at least 5,000 Da; and ii) at least one solid pesticidal active material dispersed in said aqueous medium; A concentrate formulation is provided comprising:

[0008] 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 dispersing agent in an agrochemical formulation comprising a solid agrochemical active.

[0009] According to a fourth aspect of the present invention there is provided a method of treating vegetation to control pests, the method comprising applying either to the vegetation or to the surrounding environment of the vegetation a formulation of the first aspect and / or a diluted concentrate formulation of the second aspect.

[0010] Hydrolyzed proteins have been found to provide desirable dispersion properties when used in suspension pesticide formulations with hydrophobic solid pesticide active materials. Furthermore, the hydrolyzed proteins can be obtained from sustainable sources of non-fossil fuels.

[0011] As used herein, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify a more general subject matter. Unless otherwise specified, these examples are provided solely as an aid in understanding the applications described in this disclosure and are not intended to be limiting in any way.

[0012] When describing the number of carbon atoms in a substituent (e.g., "C1-C6 alkyl"), it will be understood that the number refers to the total number of carbon atoms present in the substituent, including any carbon atoms present in any branching groups. Further, when describing the number of carbon atoms in, for example, a fatty acid, this refers to the total number of carbon atoms, including the carbon atoms in the carboxylic acid and any carbon atoms present in any branching groups.

[0013] The term "hydrolyzed protein" is used herein to mean a protein that has undergone hydrolysis. Hydrolyzed proteins may include protein fragments, polypeptides, peptides, amino acids and / or peptones.

[0014] The term "hydrolyzed protein" is used herein to include polypeptides, peptides, amino acids and / or peptones. Polypeptides, peptides and amino acids may be produced, for example, by acid hydrolysis, alkaline hydrolysis and / or enzymatic hydrolysis of native proteins. Alkaline hydrolyzed proteins are preferred. In one embodiment, hydrolyzed potato proteins are preferred, especially those produced by alkaline hydrolysis. The hydrolyzed protein component may contain carbohydrates, for example, hydrolyzed potato proteins may contain potato starch.

[0015] Hydrolyzed proteins can be produced by acid hydrolysis, alkaline hydrolysis, and / or enzymatic hydrolysis, preferably of naturally occurring proteins or proteins derived from renewable sources. Without being bound by theory, the advantage of alkaline hydrolysis compared to acid hydrolysis or enzymatic hydrolysis is that alkaline hydrolysis produces soluble hydrolyzed proteins with higher molecular weights than acid hydrolysis or enzymatic hydrolysis. Generally, acid hydrolysis can produce fragments with the smallest weight-average molecular weight, alkaline hydrolysis can produce fragments with the largest weight-average molecular weight, while enzymatic hydrolysis can produce fragments with intermediate sizes between acid hydrolysis and alkaline hydrolysis.

[0016] The size of the fragments in a hydrolyzed protein is proportional to the number of amino acid residues in the fragment, since the fragments are derived from the long amino acid chain that constitutes the unhydrolyzed protein. Alkaline hydrolysis can be advantageous for obtaining hydrolyzed proteins of desired molecular weight.

[0017] The amino compound used to make the composition of the present invention may be a partially hydrolyzed protein. The term "partially hydrolyzed protein" means a protein that has not been completely hydrolyzed, i.e., not hydrolyzed to the extent that only the individual amino acids remain in the amino compound.

[0018] The amino compounds used to make the compositions of the present invention may be chemically unmodified hydrolyzed proteins. The term "chemically unmodified hydrolyzed proteins" refers to proteins that have not been further chemically modified (or reacted) other than by hydrolysis.

[0019] Preferably, the composition does not contain protein ingredients obtained from animal protein sources. This is advantageous because animal sources may not be desirable for some consumers. Preferably, the composition does not contain animal-derived ingredients. Preferably, the composition is suitable for vegan consumers.

[0020] The hydrolyzed proteins used in the present invention are derived from plant sources or by fermentation. Preferably, they are derived from plant sources. Examples of suitable proteins include collagen, chickpea, hemp, elastin, keratin, casein, wheat protein, wheat starch, potato protein, soy protein, and / or silk protein. Potato protein, hemp protein, and chickpea protein are particularly preferred. Potato protein is especially preferred.

[0021] The hydrolyzed protein may be formed from individual amino acids or from amino acids contained within a longer peptide chain derived from the hydrolyzed protein. Preferably, the hydrolyzed protein may be an amino acid chain formed from hydrolyzing a protein.

[0022] The dispersant may be a partially hydrolyzed protein, preferably obtained from a potato, wheat, or chickpea source.

[0023] The potato, wheat, or chickpea protein source may be a potato, wheat, or chickpea protein concentrate and / or isolate. An aqueous dispersion of the potato, wheat, or chickpea protein concentrate and / or isolate may be made as a first step, and the protein may be hydrolyzed as a second step. The difference between the potato, wheat, or chickpea protein source and the partially hydrolyzed protein is that the partially hydrolyzed protein has a higher water solubility at a reference temperature (e.g., room temperature) than the potato, wheat, or chickpea protein source.

[0024] Partially hydrolyzed proteins can be produced by acid hydrolysis, alkaline hydrolysis, or enzymatic hydrolysis. Alkaline hydrolysis is preferred. One or more enzymes may be used. Preferably, the enzymes are derived from microbial sources. The enzyme(s) may include carbohydrase and / or protease. Hydrolysis may be carried out to the extent necessary to achieve the desired weight-average molecular weight of the hydrolyzed protein. The extent of hydrolysis may be varied by changing the temperature, the acid / alkali / enzyme used, and the time required. The resulting hydrolyzed protein may be filtered and / or treated to remove undesirable materials. For example, if acid hydrolysis is used, the hydrolyzed protein may be treated to remove any chloride ions present.

[0025] The molecular weight (weight average) of the protein component starting material (before hydrolysis) can vary over a wide range.

[0026] The weight average molecular weight (Mw) of the hydrolyzed potato, wheat or chickpea protein may 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 may be up to 180,000 Da, preferably up to 160,000 Da, more preferably up to 140,000 Da, especially up to 130,000 Da, and especially up to 110,000 Da.

[0027] If the hydrolyzed protein contains cross-links, the molecular weight of the hydrolyzed protein before cross-linking may be lower. The minimum range for the weight average molecular weight (Mw) of the hydrolyzed potato, wheat, or chickpea protein may be at least 3,000 Daltons (Da), preferably at least 4,000 Da.

[0028] Molecular weights are determined by size exclusion chromatography, such as size exclusion HPLC (SE-HPLC) as described herein, specifically the TSKgel GMPWXL protocol.

[0029] Hydrolysis is carried out to the extent necessary to achieve the desired molecular weight and chain length of the hydrolyzed protein. The hydrolyzed protein may be filtered and treated to remove undesirable materials.

[0030] Preferably, the hydrolyzed protein component is capable of forming an aqueous solution.

[0031] Preferably, the amount of free amino acids in the hydrolyzed protein is less than 60% by weight, more preferably less than 55% by weight, and it will be appreciated that a low amount of free amino acids is desirable due to their low solubility.

[0032] The dispersing agent may be a partially hydrolyzed protein obtained from a hemp source. The hemp protein source may be a hemp protein concentrate and / or isolate. An aqueous dispersion of the hemp protein concentrate and / or isolate may be made as a first step, and the protein may be hydrolyzed as a second step. The difference between the hemp protein source and the partially hydrolyzed protein may be that the partially hydrolyzed protein has a higher water solubility at a reference temperature (e.g., room temperature) than the hemp protein source.

[0033] Partially hydrolyzed proteins can be produced by acid hydrolysis, alkaline hydrolysis, or enzymatic hydrolysis. Alkaline hydrolysis is preferred. Hydrolysis can be carried out to the extent necessary to achieve the desired weight-average molecular weight of the hydrolyzed protein. The extent of hydrolysis can be varied by changing the temperature, the acid / alkali / enzyme used, and the time required. The resulting hydrolyzed protein can be filtered and / or processed to remove undesirable materials. For example, the hydrolyzed protein can be membrane washed to remove any salts present.

[0034] The molecular weight (weight average) of the hydrolyzed hemp protein may vary over a wide range, for example, 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 may have an average molecular weight in the range of from 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, for example about 70,000 Da.

[0035] Molecular weight is determined by size exclusion chromatography, such as size exclusion HPLC (SE-HPLC) as described herein.

[0036] The hydrolyzed protein may be copolymerized with a hydrophilic polymer. In particular, the hydrophilic polymer may 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.

[0037] More preferably, suitable hydrophilic polymers may be selected from polyvinylpyrrolidone, polyvinyl alcohol, polyglycol methacrylate (HEMA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA). Most preferably, the hydrophilic polymer is polyvinylpyrrolidone.

[0038] The protein-hydrophilic polymer copolymers used in the present invention are suitably produced by reacting a protein with a hydrophilic polymer, preferably by free radical polymerization processes known in the art.

[0039] The ratio of hydrophilic polymer to protein to react together to form the protein-hydrophilic polymer copolymer (or the ratio of hydrophilic polymer to protein present in the copolymer) is suitably in the range 2-98:2-98 wt%, preferably 5-70:30-95 wt%, more preferably 10-50:50-90 wt%, particularly 15-40:60-85 wt%, and especially 20-25:75-80 wt%.

[0040] The resulting copolymer may be of any suitable type, including a linear copolymer, such as a block copolymer, or a branched copolymer, such as a graft or star copolymer. Preferably, it may be a branched copolymer. In particular, graft copolymers may be particularly preferred.

[0041] The hydrophilic polymer used in the present invention suitably has a molecular weight (weight average) in the range of 1,000 to 40,000, preferably 5,000 to 20,000.

[0042] Hydrolyzed chickpea protein may be preferred when copolymerized with PVP and chemically modified with octenyl succinic anhydride (about 24% by weight).

[0043] The molecular weight (weight average) of the polymeric binders described herein can be determined by HPLC (SE-HPLC) as described herein, specifically the TSKgel GMPWXL protocol.

[0044] When present, the hydrophilic polymer may comprise 10 to 50% by weight of the total copolymerization reagent, preferably 13 to 35% by weight of the reagent, and more preferably 15 to 30% by weight.

[0045] Chemically modified proteins and / or hydrolyzed proteins can also be used, for example, when the protein is covalently reacted with a functional group, such as silicone or alkenyl succinic anhydride. The or each hydrolyzed protein independently may be further chemically modified, for example, when the protein is covalently reacted with said functional group.

[0046] One or more of the hydrolyzed proteins may be a chemically unmodified hydrolyzed protein. The term "chemically unmodified hydrolyzed protein" means a protein that has not been further chemically modified (or reacted) other than by hydrolysis.

[0047] The hydrolyzed polymer may be modified with more than one functional group, or the bulk hydrolyzed protein may comprise a mixture of proteins modified with different functional groups.

[0048] The modification may involve reacting at least 20%, preferably more than 30%, more preferably more than 40% of the protein with a functional group.

[0049] When present, the modifying agent may comprise 6 to 30% by weight of the total copolymerization reagents, preferably 8 to 25% by weight of the reagents, and more preferably 10 to 20% by weight.

[0050] The hydrolyzed protein may comprise cross-links. The cross-linking agent may preferably be a diglycidyl ether or a triglycidyl ether. The diglycidyl ether or the triglycidyl ether may optionally be alkoxylated.

[0051] Suitable diglycidyl ethers may 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, and are preferably selected from diglycidyl ether and neopentyl glycol diglycidyl ether.

[0052] Suitable triglycidyl ethers may be selected from castor oil glycidyl ether, trimethylolethane triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0053] In particular, when a crosslinker is selected based on a requirement for a high biobased content, a crosslinker selected from glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether, such as those available from Nagase ChemteX of Japan, may be selected. The biobased carbon content may be preferably at least 70%, more preferably at least 80%, biobased, based on the total weight of the carbon-containing portion of the composition.

[0054] The level of biobased content of a compound is: 14 It can be measured by standardized analytical method ASTM D6866 using C radiocarbon dating. ASTM D6866 distinguishes between carbon originating from biobased inputs and carbon derived from fossil-based inputs. Using this standard, the percentage of carbon derived from renewable sources can be calculated from the total carbon in a sample.

[0055] The diglycidyl ethers or triglycidyl ethers may be alkoxylated. The alkoxylation of the diglycidyl ethers or triglycidyl ethers of the present invention includes the use of oxyalkylene groups that are oxyethylene units (-CHCH-O-) and / or oxypropylene units (-CH(CH)CH-O-).

[0056] Each oxyalkylene group may contain oxyethylene, oxypropylene, or a mixture of oxyethylene and oxypropylene units. When an oxyalkylene chain contains both oxyethylene and oxypropylene, the oxyalkylene chain may be a block or random copolymer (either normal or reverse) of oxyethylene and oxypropylene units.

[0057] The number of moles of oxyethylene and oxypropylene present in each oxyalkylene group can independently be an integer ranging from 2 to 20. For example, if the value is 2, it will be understood that there are 2 moles of oxyethylene and / or oxypropylene in that particular oxyalkylene chain.

[0058] The total number of moles of oxyethylene units or oxypropylene units present in each crosslinked molecule can be an integer value in the range of 2 to 20. Preferably, it is in the range of 2 to 18. More preferably, it is in the range of 4 to 14. Even more preferably, it is in the range of 4 to 12. Most preferably, it is in the range of 6 to 10. Therefore, preferably, the oxyalkylene group is formed from 4 to 12 oxyethylene units, most preferably from 6 to 10 oxyethylene units.

[0059] When present, the crosslinking agent may comprise 4 to 55% by weight of the total copolymerization reagents, preferably 6 to 50% by weight of the reagents, and more preferably 8 to 40% by weight.

[0060] Specific preferred examples of alkoxylated diglycidyl ethers and alkoxylated triglycidyl ethers may be selected from polyethylene glycol diglycidyl ethers and polypropylene glycol diglycidyl ethers.

[0061] In particular, polyethylene glycol (500) diglycidyl ether and polypropylene glycol (380) diglycidyl ether are particularly preferred. 500 is the number average molecular weight (M n ) is understood to represent.

[0062] It is envisaged that cross-linking may be combined with copolymerisation and / or chemical modification. Preferably, the cross-linked dispersant will be based on hydrolysed proteins that are not chemically modified and are not copolymers.

[0063] A further advantage of cross-linking may be that the resulting dispersant may be biodegradable. The term "biodegradable" is used herein to mean proteins that have undergone degradation and hydrolysis. Hydrolyzed proteins may include protein fragments, polypeptides, peptides, amino acids and / or peptones.

[0064] The cross-linked hydrolyzed protein may be biodegradable, preferably at least 50% of the dispersant within a 28 day period according to OECD methods 301B and 301F, more preferably at least 60%, and most preferably at least 70%.

[0065] Thus, hydrolyzed proteins with cross-links may have the advantage of being more biodegradable and therefore more sustainable than traditional compounds used for this function.

[0066] The hydrolyzed proteins used herein without copolymerisation or modification may suitably have a molecular weight (weight average) in the range of preferably 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, especially 17,000 to 260,000.

[0067] If copolymerized, the copolymers used herein suitably have a molecular weight (weight average) in the range of preferably 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.

[0068] When copolymerized and modified, the modified copolymers used herein suitably have a molecular weight (weight average) in the range of preferably 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.

[0069] When cross-linked, the cross-linked hydrolyzed proteins used herein suitably have a molecular weight (weight average) in the range of preferably 5,000 to 800,000, preferably 5,000 to 400,000, more preferably 12,000 to 200,000, particularly 15,000 to 100,000, especially 17,000 to 260,000, and especially 30,000 to 130,000.

[0070] The molecular weight (weight average) of the polymeric binders described herein can be determined by HPLC (SE-HPLC) as described herein, specifically the TSKgel GMPWXL protocol.

[0071] The hydrolyzed protein may also contain other monomer units, in particular copolymerized monomers derived from the initiator used to make the hydrolyzed protein.

[0072] The initiator may be selected from an azo polymerization initiator or a peroxide initiator. Preferably, it may be an azo polymerization initiator. It will be understood that an azo polymerization initiator is known as a compound having an azo group (RN=N-R') that decomposes by heat and / or light to form a carbon radical, and is generally known in the polymerization field as having initiator function.

[0073] Preferred peroxide initiators may be selected from tert-butyl peroxide and hydroperoxides.

[0074] Preferably, suitable azo initiators may be water-soluble and may be 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 may be 2,2'-azobis(2-methylpropionamidine)dihydrochloride (V50).

[0075] When present, the initiator may comprise 3 to 20% by weight of the total copolymerization reagents, preferably 5 to 16% by weight of the reagents, and more preferably 7 to 12% by weight.

[0076] Preferably, the amino compound is obtained from renewable sources. The amino compound is not obtained from animal protein sources. This is advantageous because animal sources may not be desirable to consumers. Preferably, the composition does not contain animal-derived components. Preferably, the composition does not contain petrochemical-derived components.

[0077] Preferably, the carbon-containing portion of the composition is at least 40%, more preferably at least 50%, especially at least 60% bio-based according to ASTM D6866, based on the total weight of the carbon-containing portion of the composition.

[0078] The pesticide actives for use in the formulations according to the invention are solid pesticide actives. These are pesticide active compounds that are solid, which may include actives that are relatively insoluble in water at room temperature and therefore may be hydrophobic.

[0079] In the present invention, the hydrophobic solid pesticide means a substance that has extremely low solubility in water (solubility of less than 5% at 20° C. to 25° C.) or is practically insoluble.

[0080] In agrochemicals, the logarithm of the ratio of the concentrations of a non-ionized solute in two solvents, octanol and water, is used as an index of a pesticide's lipophilicity and is known as the octanol / water coefficient, logP. Pesticidal active substances can have logP values ​​in the range of 0.1 to 5, more preferably in the range of 0.3 to 2.

[0081] Agrochemical active substances, in the context of the present invention, refer to plant protection agents, more specifically biocides, which are chemicals capable of killing various forms of living organisms and are used in fields such as medicine, agriculture, forestry, and mosquito control. The group of biocides also includes so-called plant growth regulators.

[0082] Biocides used in the pesticide formulations of the present invention are typically divided into two subgroups. pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, acaricides, and rodenticides; Antimicrobial agents, including germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals, and antiparasitics.

[0083] In particular, biocides selected from insecticides, fungicides, or herbicides may be particularly preferred.

[0084] Examples of fungicides that can be used in the present disclosure include (3-ethoxypropyl)mercuric bromide, 2-methoxyethylmercuric chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercuryoxyquinoline, acibenzolar, acibenzolar-S-methyl, acipetax, acipetax copper, acipetax zinc, aldimorph, allyl alcohol, ametoctrazine, amisulbrom, ampropylphos, anilazine, aureofungin, and acibenzolar. Zaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox, bentalon, benthiavalicarb, benthiavalicarb-isopropyl, benzalkonium chloride, benzamacryl, benzamacryl-isobutyl, benzamorph, benzohydroxamic acid, bethoxadin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin S, Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture mixture), chinomethionate, clobenthiazone, chloraniformethane, chloranil, chlorphenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper zinc chromate, cresol, khuraneb, kupropam, copper oxide Copper, cyazofamid, cyclafuramide, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, dazomet sodium, DBCP, debacarb, decaphentin, dehydroacetic acid, dichlofluanid, dicloron, dichlorophen, diclozolin, diclobutrazol, diclocymet, diclomedine, diclomedine sodium, dicloran, diethofencarb, diethylpyrocarbonate,Difenoconazole, diflumetrim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6, dinoctone, dinopenton, dinosulfone, dinotervon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicin sodium, dodine, drazoxolone, edi Fenphos, epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydrochloride Cid, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Flumetober, Flumorph, Fluopicolide, Fluopyram, Fluorimide, Fluotrimazole, Fluoxastrobin, Fluquinconazole, Flusilazole, Flusulfamide, Flutianil, Flutolanil, Flutriafol, Fluxapyroxad, Folpet, Formaldehyde, Fosetyl, Fosetylaluminum, Fuberidazole, Furalaxyl, Furametpyr, Flucarbanil, Fluconazole, Fluconazole-cis, Fluf Ral, flumecyclox, furofanate, gliodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiophos, hydralgafen, hymexazole, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tribesylate, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil,Isovalerion, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzide, mepanipyrim, mepronil, meptyldinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam ammonium, metam potassium, metam sodium, metazoxolone, metconazole, metasulfocarb, metofloxam, methyl bromide, methyl isothiocyanate, methylmercuric benzoate, methylmercuric dicyandiamide, methylmercuric pentachlorophenoxy Do, metiram, metominostrobin, metrafenone, metsulfovax, milneb, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulfonanilide, nabam, natamycin, nitrostyrene, nitrotar isopropyl, nuarimol, OCH, octhilinone, ofurace, orysastrobin, oxadixyl, oxine copper, oxpoconazole, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyridine Rad, phenylmercuric urea, phenylmercuric acetate, phenylmercuric chloride, phenylmercuric derivatives of pyrocatechol, phenylmercuric nitrate, phenylmercuric salicylate, phosdifen, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin, polyoxorim, polyoxorim zinc, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazide, prothiocarb, prothiocarb hydrochloride, prothioconazole , pyracarbollide, pyraclostrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinnitrile, pyrifenox, pyrimethanil, pyriophenone, pyroquilon, pyroxchlor, pyroxiflur, quinacetol, quinacetol sulfate, quinazamide, quinconazole, quinoxyfen, quintozene, labenzazole, salicylanilide, sedaxane, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide,Sodium polysulfide, spiroxamine, streptomycin, sulfur, sultropene, TCMTB, tebuconazole, tebufloquine, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thithiofen, thifluzamide, thiochlorfenhim, thimerosal, thiophanate, thiophanate methyl, thioquinox, thiram, tiadinil, thioximide, tolclofos methyl, tolylfluanid, tolylmercuric acetate, tolyl These include, but are not limited to, azimefon, triadimenol, triamiphos, triarimol, triazbutyl, triazoxide, tributyltin oxide, triclamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole P, validamycin, valifenalate, vinclozolin, zaliramide, zinc naphthenate, zineb, ziram, zoxamide, and mixtures thereof.

[0085] Examples of insecticides that can be used in the present disclosure include 1,2-dichloropropane, abamectin, acephate, acetamiprid, acetione, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, alixycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithione, aminocarb, amiton, amiton oxalate oxalate), amitraz, anabasine, atidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azotoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluoroone, borax, boric acid , bromfenvinphos, bromocyclen, bromo-DDT, bromofos, bromophosethyl, bufencarb, buprofezin, butacarb, butathiophos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothione, carbosulfan, cartap, cartap hydrochloride , chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyphos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazofos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin Nerin II, cinerins, cismethrin, cloetocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, ciclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine,Dithioate, DDT, decarbofuran, deltamethrin, demefion, demefion-O, demefion-S, demeton, demeton methyl, demeton O, demeton O methyl, demeton S, demeton S methyl, demeton S methyl sulfone, diafenthiuron, dialifos, diatomaceous earth, diazinon, dikapton, diclofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimethane, dimethoate, dimethrin, dime Chilvinphos, Dimethilan, Zinex, Zinex-diclexine, Dinoprop, Dinosam, Dinotefuran, Diofenolan, Dioxabenzophos, Dioxacarb, Dioxathion, Disulfoton, Dicyclophos, d-Limonene, DNOC, DNOC-Ammonium, DNOC-Potassium, DNOC-Sodium, Doramectin, Ecdysterone, Emamectin, Emamectin Benzoate, EMPC, Empenthrin, Endosulfan, Endothion, Endrin, EPN, Epofenonane, Eprinomectin , esdeparethrin, esfenvalerate, ethaphos, ethiofencarb, ethion, ethiprole, ethoate methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimphos, EXD, famfur, fenamiphos, fenazaflor, fenchlorphos, fenetacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpyrithrin, fenpropathrin, fensulfothion, fenthion, fenthion ethi flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, fomiparanate, fomiparanate hydrochloride, fosmetilan, fospirate, fostietan, fufenozide, furathiocarb, fretrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,Heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hikincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazophos, isobenzane, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, iodofenphos, juvenile hormone I, juvenile hormone II, juvenile hormone Benzene III, Kelevan, Kinoprene, Lambda-cyhalothrin, Lead arsenate, Lepimectin, Leptophos, Lindane, Lilimphos, Lufenuron, Ritidathion, Malathion, Malonoben, Magidox, Mecarbam, Mecarfone, Menazone, Meperfluthrin, Mefosoran, Mercurous chloride, Mesulfenphos, Metaflumizone, Methacrifos, Methamidophos, Methidathion, Methiocarb, Metoclotophos, Methomyl, Methoprene, Methotrin, Methothrin, Methoxychlor, Methoxyfenozide, Methyl bromide, Methyl isothiocyanate, Methyl chloroform, Methyl chloride methicone, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, morosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naphthalophos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton methyl, oxydeprophos, oxydisulfoton, paradichlorobenzaldehyde parathion, parathion methyl, penfluron, pentachlorophenol, permethrin, fencapton, fenothrin, phenthoate, phorate, phosalone, phospholane, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim methyl, pyrimetaphos, pirimicarb, pirimiphos ethyl, pirimiphos methyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, profluthrin, promacyl,Promecarb, propafos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbut, pymetrozine, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, cassia (quassia), quinalphos, quinalphos-methyl, quinothione, lafoxanide, resmethrin, rotenone , Riania, Sabadila, Schradan, Selamectin, Silafluofen, Silica gel, Sodium arsenite, Sodium fluoride, Sodium hexafluorosilicate, Sodium thiocyanate, Sofamide, Spinetoram, Spinosad, Spiromesifen, Spirotetramat, Sulcofuron, Sulcofuron sodium, Sulfluramide, Sulphotep, Sulphoxaflor, Sulfuryl fluoride, Sulprofos, Taufluvalinate, Tadimcarb, TDE, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluthrin, temephos, TEPP, telalethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypei-methiin, thiacloprid, thiamethoxam, cyclofos, thiocarboxim, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap disodium, thiosultap monosodium iosultap-monosodium), thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triatene, triazamate, triazophos, trichlorfon, trichlormethaphos-3, trichloronate, tripenofos, triflumuron, trimethacarb, triplen, vamidothion, vaniliprole, XMC, xylylcarb, zetacypermethrin, zolaprofos, and mixtures thereof.

[0086] Examples of herbicides that can be used in the present disclosure include 4-CPA, 4-CPB, 4-CPP, 2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, arorac, ametridione, ametryn, amivudine, amicarbazone, amidosulfuron, aminocyclopyrachlor, and aminopyralid. , amiprophos methyl, amitrole, ammonium sulfamate, anilofos, anisrone, asuram, atraton, atrazine, azafenidine, azimsulfuron, aziprothrin, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazon, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazurone, bicyclopyrone, bifenox, viranaphos, bis Pyrivac, Borax, Bromacil, Bromobonyl, Bromobutide, Bromofenoxime, Bromoxynil, Brompyrazone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butidazole, Buthiuron, Butralin, Butroxydim, Buturon, Butyrate, Cacodylic Acid, Cafenstrole, Calcium Chlorate, Calcium Cyanamide, Cambendichlor, Carbaslam, Carbetamide, Carboxazole, Chlorprocarb, Carfentrazone, CDEA, CEPC, Chlomethoxyfen, Chloramben, Chloranocryl, Chlorhexidine Radifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim,Clopyralid, chloransulam, CMA, copper sulfate, CPMF, CPPC, cledazine, cresol, cumyluron, cyanatrin, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, dymron, dalapon, dazomet, delaclor, desmedipham, desmetrin, diallate, dicamba, dichlobenil, dichloralurea, dichloitnate, dichlorprop, dichlorprop P , diclofop, diclosulam, dietamcort, dietatyl, diphenopentene, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefron, dimepiperate, dimethachlor, dimethametrin, dimethenamid, dimethenamid P, dimexano, dimidazon, dinitramine, dinophenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamide, dipropetrin, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinadin, endothal, epronaz, EPTC , Elvon, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethidimuron, Ethiolate, Ethofumesate, Ethoxyfene, Ethoxysulfuron, Ethinofen, Ethonipromide, Ethobenzanide, EXD, Fenasulam, Fenoprop, Fenoxaprop, Fenoxaprop P, Fenoxasulfone, Fenteracol, Fentiaprop, Fentrazamide, Fenuron, Ferrous sulfate, Flamprop, Flamprop M, Flazasulfuron, Florasulam, Fluazifop, Fluazifop P, Fluazolate, Flucarbazo fluoxetine, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropin, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furiloxifene, glufosinate,Glufosinate P, glyphosate, halosafen, halosulfuron, haloxyzin, haloxyfop, haloxyfop P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobornyl, iodomethane, iodosulfuron, ioxinil, ipazine, ipfencarbazone, iprimidam, isocarbamide, isosyl, isomethiozin, isonoruron, isoporinate, isopropanol, isopropyl Proturon, Isouron, Isoxaben, Isoxachlorthor, Isoxaflutole, Isoxapyrifop, Carbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, Mecoprop, Mecoprop P, Medinoterb, Mefenacet, Mefluidid, Mesoprazine, Mesosulfuron, Mesotrione, Metam, Metamifop, Metamitron, Metazachlor, Metazosulfuron, Metoflurazon, Methabenzthiazuron, Methaproprin, Methazole, Methioben Carb, methiozolin, methiuron, methometon, metoprothrin, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metoslam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morphamcort, MSMA, naproanilide, napropamide, naptalam, nebulon, nicosulfuron, nipiraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, norlon, OCH, O Rubencarb, orthodichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluorone, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, petoxamide, phenisopham, phenmedipham, phenmedipham ethyl, fenobenzuron, phenylmercuric acetate, picloram, picolinafen, pinoxaden,Piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazin, prodiamine, profluazole, profluralin, profoxydim, proglinadin, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfarin, prosulfocarb, prosulfuron, proxan, prinachlor, pidanone, pyraclonil, pyraflufen, pyra Sulfotole, pyrazolinate, pyrazosulfuron, pyrazoxifen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quinonamide, quizalofop, quizalofop P, rhodetanil, rimsulfuron, saflufenacil, S-metolachlor, sebutylazine, secbumeton, sethoxydim, siduron , simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfurate, sulfentrazone, sulfometuron, sulfosulfuron, sulfate, sulglicapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoroone, thenylchlor, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencal Examples of suitable antibacterial agents include bazonemethyl, thifensulfuron, thiobencarb, thiocarbazil, thioclorim, topramezone, tralkoxydim, triallate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphan, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, triphop, trifopsim, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vemolate, xylaclor, and mixtures thereof.

[0020] Safener refers to an active ingredient applied together with a herbicide to protect crops from damage. Some safeners that can be used in the present disclosure include, but are not limited to, benoxacor, benthiocarb, brassinolide, cloquintocet (mexyl), cyometrinil, dymron, dichlormid, dicyclonone, dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148, N-phenylsulfonylbenzoic acid amide, and mixtures thereof.

[0087] Most preferably, the active substance present in the pesticide formulation of the present invention may be selected from imidacloprid, diflufenican, azoxystrobin, or trifloxystrobin.

[0088] Agrochemically active compounds, including insecticides and fungicides, require formulations that allow the active compound to be taken up by the plant / target organism.

[0089] As used herein, the term "pesticidal formulation" refers to a composition containing an active pesticide and is intended to include compositions in all forms, including concentrates and spray formulations. Unless otherwise specified, the pesticide formulations of the present invention may be in the form of a concentrate, a diluted concentrate, or a sprayable formulation.

[0090] The dispersants of the present invention can be combined with other ingredients to form pesticide formulations containing at least one pesticidal active.

[0091] The formulation of the present invention is a water-based suspension formulation.In the form of concentrate, they are generally used to disperse water-insoluble active ingredients, and the dispersion is directly present in the aqueous phase, or absorbed or adsorbed on a solid support, or the active substance is present as a microencapsulated liquid or solution.These are generally known as suspension concentrates (SC), in which the active compound is present as a solid.

[0092] Additionally, the formulations of the present invention may be suspoemulsions (SEs), which combine two active ingredients with different physical properties in one formulation, including a dispersion of an insoluble solid active agent in water and a dispersion of a water-insoluble liquid or a solution of a solid dissolved in oil.

[0093] Aqueous pesticide concentrates are pesticide compositions designed to be diluted with water (or a water-based liquid) to form a corresponding spray formulation.

[0094] Spray formulations are aqueous pesticide formulations that contain all the ingredients desired to be applied to plants or their environment. Spray formulations can be made by simple dilution of a concentrate containing the desired ingredients (except water).

[0095] Thus, the dispersant may be incorporated into the formulation of the pesticidal active compound (in-can / built-in formulation).

[0096] Depending on the customer's needs, the concentrate thus formed can typically contain up to 95% by weight of the pesticidal active. The concentrate can be diluted for use to obtain a diluted composition having a pesticidal active concentration of about 0.5% to about 1% by weight. The diluted composition (e.g., spray application rates of 10 to 500 l / ha) can be used. -1 In spray formulations, which may be spray formulations, the pesticidal active concentration may range from about 0.001% to about 1% by weight of the total formulation sprayed.

[0097] The dispersants of the present invention are typically used in an amount proportional to the amount of active pesticide in the formulation. In pesticide formulation concentrates, the proportion of dispersant depends on the solubility of the components in the liquid carrier. Typically, the concentration of dispersant in such concentrates is 1% to 20% by weight, preferably 1.5% to 10% by weight, and more preferably 2% to 5% by weight.

[0098] The weight ratio of dispersant to active pesticide in concentrate and diluted concentrate pesticide formulations is preferably from about 0.05:1 to about 0.2:1, and more preferably from about 0.7:1 to about 0.15:1. This ratio range is generally maintained in concentrate forms of the formulation (e.g., when the adjuvant is included in a dispersible liquid concentrate or dispersible solid granule formulation) and in spray formulations.

[0099] When a concentrate (solid or liquid) is used as the source of the active pesticide and / or dispersant, the concentrate is typically diluted to form the spray formulation. Dilution can be with 1 to 10,000 times, and more particularly 10 to 1,000 times, the total weight of the concentrate with water to form the spray formulation.

[0100] When the pesticidal active is present as a solid particle in the aqueous end-use formulation, it is most often present primarily as particles of the active pesticide. However, if desired, the active pesticide can be supported on a solid carrier, such as silica or diatomaceous earth, which can be the solid carrier, filler, or diluent materials described above.

[0101] Spray formulations typically have a pH ranging from moderately acidic (e.g., about 3) to moderately alkaline (e.g., about 10), particularly near neutral (e.g., about 5 to 8). More concentrated formulations have a similar degree of acidity / alkaline, but because they may be primarily non-aqueous, pH is not necessarily an appropriate measure of their effectiveness.

[0102] One problem with solid active materials is, for example, crystal growth of the active ingredient during relatively short periods of storage due to "Ostwald ripening." Crystal growth due to "Ostwald ripening" typically occurs when small crystals (which have a higher surface area than larger crystals) dissolve in the aqueous phase and transport the material through the continuous phase to nucleation sites for larger crystals.

[0103] As a result, crystals of the active ingredient may aggregate and settle, resulting in a non-homogeneous formulation, clogging of spray equipment filters and nozzles during application, and reduced biological efficacy. In aqueous suspension concentrates, the purpose of the dispersant is to prevent excessive growth of crystal size.

[0104] The dispersants of the present invention have also been found to be effective in slowing and / or arresting crystal growth of active ingredients that have a tendency to grow crystals by "Ostwald ripening".

[0105] In particular, dispersant combinations are useful for inhibiting crystal growth of certain lipophilic active substances, i.e., active substances that are hydrophobic and poorly dispersible. In agrochemicals, the logarithm of the ratio of the concentrations of a non-ionized solute in two solvents, octanol and water, is used as an indicator of the lipophilicity of a pesticide, known as the octanol / water coefficient, Ko / w, or logP. The polymers of the present invention enable the preparation of aqueous pesticide formulations containing 50 to 1100 g / L of at least one pesticide with a logP of -1.5 to +6.

[0106] The formulation may also include additional ingredients selected from pigments, dyes, micronutrients, pesticide actives, bulking agents, and combinations thereof.

[0107] The pesticide formulation may contain, in conjunction with the primary adjuvant and coadjuvant, a solvent (other than water), such as monopropylene glycol, an oil, which may be a vegetable oil or a mineral oil, e.g., a spray oil (an oil included in a spray formulation as a non-surfactant adjuvant). Such a solvent may be included as a solvent for the adjuvant and / or as a humectant, e.g., propylene glycol, in particular. When used, such a solvent is typically included in an amount of 5% to 500% by weight, preferably 10% to 100% by weight, based on the weight of the adjuvant. Such combinations may also include salts, such as ammonium chloride and / or sodium benzoate, and / or urea, among others, as gel inhibition aids.

[0108] The pesticide formulation may optionally contain other ingredients. These other ingredients may be selected from: Binders, especially those that dissolve readily in water and result in low viscosity solutions at high binder concentrations, such as polyvinylpyrrolidone; polyvinyl alcohol; carboxymethylcellulose; gum arabic; sugars, such as sucrose or sorbitol; starch; ethylene-vinyl acetate copolymers, sucrose, and alginates. 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; and sodium benzoate, etc. Disintegrants, such as surfactants, materials that swell in water, such as carboxymethylcellulose, collodion, polyvinylpyrrolidone, and microcrystalline cellulose swelling agents; salts, such as sodium or potassium acetate, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, ammonium sulfate, and dipotassium hydrogen phosphate; Wetting agents, such as alcohol ethoxylate and alcohol ethoxylate / propoxylate wetting agents; Dispersants, such as sulfonated naphthalene formaldehyde condensates and acrylic acid copolymers, such as comb copolymers having polyethylene glycol side chains capped onto a polyacrylic acid backbone; emulsifiers, such as alcohol ethoxylates, ABA block copolymers, or castor oil ethoxylates; an antifoaming agent, such as a polysiloxane antifoaming agent, typically in an amount of 0.005% to 10% by weight of the formulation; viscosity modifiers, such as commercially available water-soluble or miscible gums, e.g., xanthan gum, and / or cellulose-based ones, such as carboxy-, methyl-, ethyl-, or propyl-cellulose; and / or Preservatives and / or antimicrobial agents, such as organic acids or their esters or salts, for example ascorbic acid-based agents such as ascorbyl palmitate, sorbic acid-based agents such as potassium sorbate, benzoic acid-based agents such as benzoic acid and methyl and propyl 4-hydroxybenzoate, propionic acid-based agents such as sodium propionate, phenolic agents such as sodium 2-phenylphenate; 1,2-benzisothiazolin-3-one; or formaldehyde itself or paraformaldehyde; or inorganic materials such as sulfurous acid and its salts, typically in an amount of 0.01% to 1% by weight of the formulation.

[0109] The pesticide formulations according to the invention may include ingredients such as surfactants which form part of the emulsifier system. The surfactants may include surfactant dispersants.

[0110] Adjuvants may be included in and used in the compositions and formulations of the present invention. Examples include alkyl polysaccharides (more appropriately 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.

[0111] The formulation may include at least one nutrient, which refers to chemical elements and compounds that are desirable or necessary to promote or improve plant growth.

[0112] Nutrients are generally described as macronutrients or micronutrients. Nutrients suitable for use in concentrates according to the present invention are micronutrient compounds, preferably those that are solid or partially soluble at room temperature.

[0113] Micronutrients typically refer to trace metals or trace elements, and are often applied in low doses.Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum, and manganese.It is envisioned that the dispersant of the present invention is widely applicable to all types of micronutrients.

[0114] The micronutrients may be in soluble form or may be included as insoluble solids, and may be in the form of salts or chelates. Preferably, the micronutrients are in the form of carbonates or oxides.

[0115] Preferably, the micronutrient may be selected from zinc, calcium, molybdenum or manganese, or magnesium. Particularly preferred micronutrients for use in the present invention may be selected from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0116] The amount of micronutrient in the concentrate is typically 5% to 40% by weight, more usually 10% to 35% by weight, especially 15% to 30% by weight, based on the total concentrate.

[0117] Typically, when mixed into a formulation during manufacture, the solid pesticide has an average particle size of 50 m to 100 m, but the formulation is typically wet-milled after mixing to reduce the average particle size to 1 m to 10 m, more preferably 1 m to 5 m.

[0118] The formulation of the present invention may also contain at least one macronutrient. Macronutrients typically refer to those containing nitrogen, phosphorus, and potassium, including fertilizers and water conditioners such as ammonium sulfate. Suitable macronutrients include fertilizers and other nitrogen-, phosphorus-, or sulfur-containing compounds, and water conditioners.

[0119] Suitable fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium, or sulfur. Examples of such fertilizers include: For nitrogen as a nutrient: nitrates and / or ammonium salts such as ammonium nitrate (including, for example, in combination with urea as a uranium-type material), calcium ammonium nitrate, ammonium nitrate sulfate, ammonium phosphates, especially monoammonium phosphate, diammonium phosphate and ammonium polyphosphate, ammonium sulfate, and less commonly calcium nitrate, sodium nitrate, potassium nitrate, and ammonium chloride; For phosphorus as a nutrient: phosphorus in its acidic form, such as phosphate, pyrophosphate, or polyphosphate, but more commonly in its salt form, such as ammonium phosphate, especially monoammonium phosphate, diammonium phosphate, and ammonium polyphosphate, potassium phosphate, especially potassium dihydrogen phosphate and potassium polyphosphate; For sulfur as a nutrient: ammonium sulfate and potassium sulfate, mixed sulfates with e.g. magnesium.

[0120] Biostimulants may promote 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 (e.g., ascophyllum nodosum), humic acids (e.g., potassium humate), fulvic acid, myo-inositol, glycine, and combinations thereof.

[0121] The present invention further includes a method of treating plants using the formulation of the first aspect.

[0122] Thus, the present invention further includes methods of use, including: a method of killing or suppressing vegetation by applying to the vegetation or the surrounding environment of the vegetation, e.g., the soil surrounding the vegetation, a spray formulation comprising at least one dispersed phase pesticide and an adjuvant of the first aspect; and / or 1. A method of killing or controlling plant pests by applying to the plant or the plant's surrounding environment, for example the soil surrounding the plant, a spray formulation comprising one or more pesticides, for example at least one dispersed phase pesticide which is an insecticide, fungicide or acaricide, and an adjuvant of the first aspect.

[0123] As used herein, the term "dispersant" or "dispersible" refers to a compound that, when added to a pesticide formulation, improves the desired effect of the pesticide. Dispersants may affect the diluent, mixture, active, or target by improving the performance of the active.

[0124] Preferably, the dispersants of the present invention can be used as either the sole component or the primary dispersancy functioning agent when formulated directly into pesticide concentrates.

[0125] The materials of the present invention are more easily diluted in agricultural concentrates and exhibit lower fluid viscosities in aqueous systems when diluted in concentrates or with water before spraying. This behavior improves ease of use of products containing them, both during manufacture and dilution, especially in cold water. Reduced foam stability is also observed, thereby reducing the need for foam control agents. The dispersants of the present invention can be added to pesticide formulations without causing undesirable thickening or destabilization.

[0126] It will be appreciated that the particle size and distribution are factors that reflect the stability of a dispersion since the dispersion contains particles of a solid with low water solubility.

[0127] Uniform particle distribution is important to ensure dispersion stability over time. Furthermore, an effective dispersant prevents particles from clumping together and causing phase separation. Therefore, dispersions with small particle size, uniform particle distribution, and limited particle size growth over time are likely to be more stable.

[0128] In the form of a particle size distribution, particles have a median volume particle diameter value. The median volume particle diameter value will be understood to refer to the equivalent spherical diameter corresponding to the point on the distribution that divides the population exactly in half. This is the point corresponding to 50% of the volume of all particles and is read on a cumulative distribution curve that shows the relationship between volume percentage and particle diameter. That is, 50% of the distribution is above this value and 50% is below this value. This value is referred to as the "D(v,0.5)" value and is determined as described herein.

[0129] Additionally, one may refer to the "D(v,0.9)" value, which is the equivalent spherical diameter corresponding to 90% of the volume of all particles, and is read on the cumulative distribution curve that shows the relationship between volume percentage and particle diameter, i.e., the point where 10% of the distribution is above this value and 90% is below this value.

[0130] The particle size values ​​used to determine the D(v,0.5) and D(v,0.9) values ​​are measured by techniques and methods described in more detail herein. It will be understood that the particle size values ​​defined below are based on 2-3.5 wt. % total dispersant, as shown in the examples.

[0131] It is generally known that a particle size of 1 to 10 μm is preferable to obtain a dispersion liquid with desired properties.

[0132] The particles present in the dispersant of the present invention may have an initial D(v,0.5) value on day 0 in the range of 2.5 μm to 8.0 μm, preferably in the range of 3.0 μm to 7.0 μm, more preferably in the range of 3.2 μm to 6.0 μm, and most preferably in the range of 3.3 μm to 6.0 μm.

[0133] The particles present in the dispersant of the present invention may have a D(v,0.9) value on day 0 in the range of 5.0 μm to 14.0 μm, preferably in the range of 5.5 μm to 12.0 μm, and more preferably in the range of 6.0 μm to 11.0 μm.

[0134] The particles present in the dispersant of the present invention may have a D(v,0.5) value at 7 days and 54°C in the range of 1.0 μm to 20.0 μm, preferably in the range of 2.0 μm to 18.0 μm, more preferably in the range of 3.0 μm to 15.0 μm, and most preferably in the range of 3.5 μm to 13.0 μm.

[0135] The particles present in the dispersant of the present invention may have a D(v,0.9) value at 7 days and 54°C in the range of 5.0 μm to 75.0 μm, preferably in the range of 6.0 μm to 65.0 μm, more preferably in the range of 7.0 μm to 62.0 μm, and most preferably in the range of 9.0 μm to 60.0 μm.

[0136] The particles present in the dispersant of the present invention, when maintained at 54°C, exhibit a change in either or both of D(v,0.5) and D(v,0.9) of 150% or less, preferably 130% or less, and most preferably 110% or less, between 0 and 7 days.

[0137] This allows the dispersants of the present invention to provide good particle size and particle size distribution within the range desired for suspension concentrates. Furthermore, the suspensions of the present invention maintain the desired particle size and particle size distribution even upon prolonged storage, i.e., there is little or no decrease in particle size over time.

[0138] All features described herein may be combined with any of the above aspects in any combination.

[0139] In order that the present invention may be more readily understood, reference is now made, by way of example, to the following descriptions.

[0140] It will be understood that all tests and physical properties listed were determined at atmospheric pressure and room temperature (i.e., 25°C) unless otherwise specified herein or in the referenced test methods and procedures. [Example]

[0141] The following test methods were used to determine the performance of the dispersant compositions.

[0142] 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 3000 SM attachment, set at 2,500 rpm and running with deionized water. The refractive index of the material was set according to the following criteria at an absorbance of 0.1, and data were acquired using 15,000 snaps taken over 15 seconds. From the particle size values ​​obtained, the D(v0.5) and D(v0.9) values ​​were easily determined.

[0143] Refractive index reference values: a refractive index of 1.713 was used for imidacloprid and a refractive index of 1.511 for trifloxystrobin.

[0144] Stability - The stability of all formulations was evaluated after specified periods at room temperature (RT, 25°C) and 54°C. All samples were visually evaluated to determine any precipitation / creaming that may have occurred.

[0145] Suspension - Samples were evaluated according to CIPAC MT 161. In this method, 250 ml of aqueous diluted suspension concentrate is prepared by mixing by inverting a graduated cylinder 30 times, and allowed to stand in the cylinder under specified conditions for a specified time (30 minutes), and the top nine-tenths is removed. The remaining one-tenth is then assayed either chemically, gravimetrically, or by solvent extraction. This method gives an indication of the stability of the homogeneity of the diluted suspension concentrate over time. Complete stability of homogeneity corresponds to 100%.

[0146] pH was measured as a concentrate formulation according to CIPAC MT 75.

[0147] The weight-average molecular weight was determined by size-exclusion high-performance liquid chromatography (SE-HPLC). The HPLC equipment and settings used are shown below.

[0148] [Table 1] How to synthesize the resulting material: Method for Hydrolyzed Potato Protein (C7) Potato protein isolate powder was dispersed in water. Peracetic acid was added to the slurry, and the slurry was stirred for 24 hours. The peracetic acid was removed from the solution by repeatedly washing the precipitate with fresh water. The acid-treated potato slurry was then raised to a pH of >12.5 using NaOH (25%). The slurry was then stirred for 24 hours, after which the pH was lowered to 9.0 and undissolved material was removed. Soluble protein was then precipitated at pH 4, and the precipitate was washed with fresh water. After washing, the precipitate was dissolved by raising the pH to 6 using NaOH (25%). The solution was then stored to prevent microbial growth.

[0149] Method for potato protein (C1) Potato protein (400 g) was mixed with water (2800 g) and heated to 40°C. NaOH (25%, 250 g) was added and the reaction was stirred at that temperature for 22 hours. Hydrogen peroxide (35%, 34.5 g) was added and the reaction was stirred for 45 minutes, after which the peroxide addition was repeated. The reaction was stirred for 1 hour and 15 minutes, after which the heat was removed and HCl (28%) was added to lower the pH to 9.5. The reaction was filtered to remove insoluble material. This material was adjusted to pH 4.0 with HCl (28%) to precipitate the protein. The reaction volume was increased to 5000 ml with water. The protein was allowed to settle overnight, after which the water was removed and the solid was redissolved by raising the pH to 6.0 with NaOH (25%). The final product was saved and then filtered.

[0150] Hydrolyzed potato protein (250 g) was mixed with vinylpyrrolidinone (15.0 g) and heated to 85°C. In a separate 50 mL beaker, 4,4'-azobis(4-cyanovaleric acid) (5.0 g) was added to 25 mL of distilled water. The pH of the initiator solution was raised to 6.0 by slowly stirring in NaOH (25%) to dissolve the powder. Once dissolved, the initiator solution was fed to the reaction over 3 hours. After the initiator feed was complete, the reaction was stirred at that temperature for an additional 3 hours. The reaction was cooled and then filtered.

[0151] Method for Potato Protein / Polyvinylpyrrolidone (C2) Preparation of base hydrolysate - Potato protein isolate (100 g) was added to a 1-liter beaker along with water (500 g). The slurry was mixed and heated to 40°C. To the slurry, 75 g of 25% NaOH was added, and the reaction was covered and stirred for 22 hours. 6 g of 35% hydrogen peroxide was then added, followed by 6 g of 35% hydrogen peroxide after 1 hour. The reaction was stirred for 1 hour, after which the pH was lowered to 10 by adding 28% HCl. Insoluble material was removed by centrifugation, and the protein was precipitated at pH 4.0 by adding 28% HCl. The precipitate was washed with fresh water and then redissolved by adding 25% NaOH to raise the pH to 6.2. The protein solution was stored to prevent microbial growth.

[0152] To copolymerize with vinylpyrrolidinone, a solution of hydrolyzed protein (as described above) (200.2 g) and vinylpyrrolidinone (13.65 g) was added to a 400 ml beaker. The solution was stirred magnetically and heated to 75°C. A separate solution of V-50 initiator, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (5.44 g) in water (25 g), was fed into the protein / monomer solution over 3 hours. After the feeds were completed, the lines were flushed with water (10 g). The reaction was covered and stirred at room temperature for an additional 3 hours before being cooled to room temperature. After cooling, the solution was filtered to remove any precipitate.

[0153] All protein-PVP samples were made using the same method but with varying monomer and initiator concentrations.

[0154] Method for potato protein copolymer (C3) To make the base protein hydrolysate, potato protein (200 g) was mixed with water (1400 g) and heated to 50° C. NaOH (25%, 125 g) was added. The slurry was stirred at that temperature for 6 hours, after which the heat was removed 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. The slurry was then filtered to remove insoluble material.

[0155] To modify with OSA, a portion of the hydrolyzed protein (854 g) was heated to 40°C and N-octenylsuccinic anhydride (10 g) was added. The pH was maintained at 10.0-10.5 for 6 hours, after which HCl (28%) was added to lower the pH to 4. The solid was allowed to settle 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 saved and filtered.

[0156] To prepare the VP copolymer, 200 g of modified potato protein was mixed with 14.3 g of vinylpyrrolidinone and heated to 85°C. A solution of 5.7 g of 4,4'-azobis(4-cyanovaleric acid) in 35 g of water was adjusted to pH 6.5 and fed to the reaction mixture over 3 hours. The reaction mixture was then allowed to react for an additional 3 hours before being cooled.

[0157] Method for Chickpea Protein Copolymer (C4) Preparation of base hydrolysate - Chickpea protein isolate (200 g) was stirred in water (1000 g) in a 2 liter beaker. The slurry was heated to 45°C and NaOH (25%, 150 g) was added. The reaction was covered and stirred for 21 hours. HCl (28%) was added to lower the pH to 10 and the slurry was filtered to remove insoluble material. HCl (28%) was then added to precipitate the protein at pH 4.0. The precipitate was washed with fresh water before the solid was redissolved by raising the pH to 10.2 with NaOH (25%).

[0158] To modify with OSA, a solution of hydrolyzed protein (as described above) (300 g) was added to a 600 ml beaker and heated to 40°C. The pH of the solution was raised to pH 10.2 using NaOH (25%). N-octenyl succinic anhydride (15.0 g) was added over 30 min. The pH was maintained at 10.0-10.2 during the addition and for 4 h thereafter. After this, the pH was lowered to 6.5 by adding HCl (28%). The product was stirred overnight to dissolve any precipitate that had formed during the pH adjustment. To copolymerize with vinylpyrrolidinone, a solution of the modified hydrolyzed protein (200 g) and vinylpyrrolidinone (10.0 g) was added to a 400 ml beaker. The solution was stirred magnetically and heated to 75°C. A separate solution of V-50 initiator, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (4.0 g) in water (20 g), was fed into the protein / monomer solution over a 3-hour period. After the feeds were completed, the lines were flushed with water (10 g). The reaction was covered and stirred at room temperature for an additional 3 hours before being cooled to room temperature. After cooling, the solution was filtered to remove any precipitate.

[0159] Method for Hemp Protein Copolymer (C5) Preparation of base hydrolysate - In a 1 liter beaker, hemp protein isolate (150 g) and water (600 g) were mixed. The slurry was heated to 45°C and NaOH (25%, 95 g) was added. The slurry was covered and stirred at that temperature for 21 hours. HCl (28%) was then added to lower the pH of the reaction to 10.0. The slurry was then centrifuged to remove insoluble material, which was then precipitated at pH 4.0 by the addition of HCl (28%). The precipitate was washed with fresh water and then redissolved at pH 6 by the addition of NaOH (25%). The hydrolyzed protein was then stored to prevent microbial growth.

[0160] Vinylpyrrolidinone copolymerization—A solution of the modified hydrolyzed protein (100 g) and vinylpyrrolidinone (5.0 g) from above was added to a 250 ml beaker. The solution was stirred magnetically and heated to 75°C. A separate solution of V-50 initiator, 2,2′-azobis(2-methylpropionamidine) dihydrochloride (2.0 g) in water (15 g), was fed into the protein / monomer solution over 3 hours. After the feeds were completed, the lines were flushed with water (5 g). The reaction was covered and stirred at room temperature for an additional 3 hours before being cooled to room temperature. After cooling, the solution was filtered to remove any precipitate.

[0161] Method for quaternizing degraded potato protein (C6) In a 600 ml beaker, hydrolyzed protein (C8) (400 g) was adjusted to pH 10.2 using NaOH (25%). The solution was heated to 40° C. and 2,3-epoxypropyltrimethylammonium chloride (70%, 9.0 g) was added. The pH of the reaction was maintained with NaOH (25%) for 4 hours, after which the pH was reduced to 6.5 by the addition of HCl (28%).

[0162] Method for cross-linking wheat protein (C8) with PEG500DGE Wheat protein (400 g) was mixed with water (1600 g) and heated to 40°C. NaOH (25%, 248 g) was added and the reaction was stirred for 20 hours. Hydrogen peroxide (22.5 g) was added and the reaction was stirred for 1 hour, after which the peroxide addition was repeated. HCl (28%) was added to lower the pH of the solution to 10.5. The hydrolysate was filtered to remove insoluble material and then concentrated by evaporation. To crosslink, hydrolyzed wheat protein (20.6% actives, 300 g) was heated to 60 °C. PEG500DGE (6 g) was added to the reaction, and after 30 min, an additional PEG500DGE (3 g) was added. The reaction was maintained between 10.0 and 10.4 for 6 h. The pH was reduced to 6.0 by adding HCl (28%) and stored.

[0163] Method for cross-linking potato protein (C9) with PEG500DGE Potato protein (100 g) was stirred in water (700 g) and heated to 60°C. NaOH (25%, 65 g) was added. The high-pH reaction was stirred for 6 hours, after which HCl (28%) was added to lower the pH to 11.0. Heating was stopped, and hydrogen peroxide (8.6 g) was added. After 30 minutes, the peroxide addition was repeated. The material was filtered to remove insoluble material. The cloudy solution was then heated to 60°C, and PEG500DGE (10 g) was added. The pH was maintained at 10.0-10.4 using NaOH (25%). After 1 hour, the PEG500DGE addition was repeated, and the reaction was stirred at that temperature for 24 hours. After 24 hours, the pH was lowered to 5.5, and the final material was evaporated to an RI of 30 and stored.

[0164] Method for cross-linking wheat proteins (C10) with NPDGE Potato protein (400 g) was mixed with water (2800 g) and heated to 40°C. NaOH (25%, 250 g) was added and stirred at that temperature for 22 hours. Hydrogen peroxide (35%, 34.5 g) was added and the reaction was stirred for 45 minutes, after which the peroxide addition was repeated. The reaction was stirred for 1 hour and 15 minutes, after which the heat was removed and HCl (28%) was added to lower the pH to 9.5. The reaction was filtered to remove insoluble material. A portion of this material (600 g) was heated to 60°C and adjusted to pH 10.5. NPDGE (6.5 g) was added, and after 1 hour, an additional amount of NPDGE (6.5 g) was added. The reaction was then stirred at 40°C for 18 hours. The pH of the reaction was then lowered to 4.0 with HCl (28%) to precipitate the cross-linked protein. The aqueous layer was removed, and the solid was redissolved by raising the pH to >6. The final product was saved.

[0165] Method for cross-linking potato proteins (C11) with NPDGE Base protein hydrolysate—potato protein (400 g) was mixed with water (2800 g) and heated to 40°C. NaOH (25%, 250 g) was added and stirred at that temperature for 22 hours. Hydrogen peroxide (35%, 34.5 g) was added and the reaction was stirred for 45 minutes, after which the peroxide addition was repeated. The reaction was stirred for 1 hour and 15 minutes, after which the heat was removed and HCl (28%) was added to lower the pH to 9.5. The reaction was filtered to remove insoluble material. This material was adjusted to pH 4.0 with HCl (28%) to precipitate the protein. The reaction volume was increased to 5000 ml with water. The protein was allowed to settle overnight, after which the water was removed and the solid was redissolved by raising the pH to 6.0 with NaOH (25%). The reaction was then stored. Cross-linked hydrolyzed potato protein (150 g) was heated to 60°C and adjusted to pH 10.2. NPDGE (1.5 g) was added and the reaction was stirred at that temperature and controlled pH for 24 hours. The product was then precipitated at pH 4 using HCl (28%). The aqueous layer was removed and the solid was redissolved at pH 6 and stored.

[0166] Method for cross-linking wheat proteins (C12) with NPDGE Wheat protein (100 g) was mixed with water (700 g) and heated to 40° C. 25% NaOH (65 g) was added and the reaction was stirred for 18 hours. Insoluble material was removed by filtration, the pH was adjusted to pH 10.2, heated to 60° C., and NPDGE (20 g) was added. The reaction was stirred for 18 hours before precipitation at pH 2.0. The solid was collected, redissolved at pH 6.0, and stored.

[0167] Method for cross-linking potato protein (C13) with BDGE Potato protein (200 g) was mixed with water (1400 g) and heated to 50°C. NaOH (25%, 125 g) was added. The slurry was stirred at that temperature for 6 hours, after which the heat was removed and hydrogen peroxide (35%, 16.5 g) was added. After 20 minutes, HCl (28%) was added to lower the pH to 10, and the peroxide addition was repeated. The slurry was then filtered to remove insoluble material. A portion of the hydrolyzed protein (860 g) was heated to 60°C and BDGE (10 g) was added. After 1 hour, the addition of BDGE (10 g) was repeated, and the reaction was stirred for 6 hours. The pH was maintained between 10.0 and 10.5 throughout. The pH of the solution was lowered to 4.0 to precipitate the protein. The aqueous layer was removed, and the solid layer was redissolved by raising the pH to 6.4 with NaOH (25%) and saved.

[0168] Generated materials Following the methods detailed above, the following hydrolyzed proteins were produced for testing: C1 - Potato protein / polyvinylpyrrolidone copolymer, molecular weight approximately 196,000 daltons, activity approximately 16% C2 - Potato protein / polyvinylpyrrolidone copolymer, molecular weight approximately 18,000 daltons, activity approximately 17.5% C3-Potato protein / octylsuccinic anhydride polyvinylpyrrolidone copolymer, molecular weight approximately 43,000 daltons, activity approximately 21% C4-Chickpea protein / Octylsuccinic anhydride polyvinylpyrrolidone copolymer, molecular weight approximately 38,000 daltons, activity approximately 24% C5-hemp protein / polyvinylpyrrolidone copolymer, molecular weight approximately 159,000 daltons, activity approximately 22% C6-Quaternized potato protein, molecular weight approximately 10,200 daltons, activity approximately 14% C7-hydrolyzed potato protein, molecular weight approximately 71,000 daltons, activity approximately 11% Wheat protein cross-linked with C8-PEG500DGE, molecular weight approximately 50,850 daltons, activity approximately 21.3% Potato protein cross-linked with C9-PEG500DGE, molecular weight approximately 21,095 daltons, activity approximately 20.8% Potato protein cross-linked with C10-NPDGE, molecular weight approximately 90,128 daltons, activity approximately 14.19% Potato protein cross-linked with C11-NPDGE, molecular weight approximately 52,294 daltons, activity approximately 20.45% Wheat protein cross-linked with C12-NPDGE, molecular weight approximately 34,832 daltons, activity approximately 16% Potato protein cross-linked with C13-BDGE, molecular weight approximately 77,000 daltons, activity approximately 19% NPDGE - Neopentyl glycol diglycidyl ether.

[0169] PEG500DGE - Polyethylene glycol (500) diglycidyl ether.

[0170] BDGE-Butylene glycol diglycidyl ether VP-N-vinylpyrrolidinone Tests with imidacloprid The copolymer formed above was used to formulate a 550 g / L imidacloprid suspension concentrate (SC) with low amounts of dispersant and wetting agent according to Table 1 below, where xanthan gum (typically used for structuring) was omitted.

[0171] [Table 2] Test using trifloxystrobin The copolymer formed above was used to formulate 500 g / L trifloxystrobin SC with low amounts of dispersing and wetting agents according to Table 2 below, where xanthan gum (typically used for structuring) was omitted.

[0172] [Table 3] Test using diflufenican The dispersant formed above was used to formulate 500 g / L diflufenican SC with low amounts of dispersant and wetting agent according to Table 3 below, where xanthan gum (typically used for structuring) was omitted.

[0173] [Table 4] result The formulations (imidacloprid, trifloxystrobin, and diflufenican) were then tested at room temperature (RT) and 54°C for 7 days as shown in the test schedule in Table 3 below. [Table 5] The results obtained are shown in Tables 5 to 8 below.

[0174] [Table 6] [Table 7] [Table 8] [Table 9] biodegradation The samples were tested for biodegradability and the results were obtained in relation to OECD standards as shown in Table 9.

[0175] [Table 10] The results obtained are shown in Table 10.

[0176] [Table 11] All samples tested showed a high level of biodegradability.

[0177] This protein exhibits excellent performance in terms of suspension and storage stability. Particle size performance is well controlled over 7 days, preventing aggregation and limiting growth, with a D(0.9) of less than 10 microns. Furthermore, good rheological performance was observed.

[0178] It should be understood that the invention is not limited to the details of the above embodiments, which are given by way of example only. Many variations are possible.

Claims

1. A suspension-type aqueous pesticide formulation, i) a dispersant of hydrolyzed vegetable protein having a molecular weight of at least 5,000 Da; and ii) at least one solid pesticidal active dispersed in said aqueous medium. A suspended aqueous pesticide formulation comprising:

2. 10. The formulation of claim 1, wherein the hydrolyzed proteins are derived from potato protein, hemp protein, and chickpea protein.

3. 3. The formulation of 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. A formulation according to any one of claims 1 to 3, wherein the hydrolysed protein is derived from potato protein.

5. 5. The formulation of any one of claims 1 to 4, wherein the hydrolyzed protein is copolymerized with a hydrophilic polymer selected from polyvinylpyrrolidone (PVP), polyvinyl alcohol, polyvinyl alcohol copolymer, polyglycol alkyl acrylate, polyether, polyether alkyl methacrylate, polyvinyl acetate, and polyvinyl acetate copolymer.

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

7. 7. The formulation of any one of claims 1 to 6, wherein the hydrolyzed protein is chemically modified by covalently reacting it with a functional group selected from silicone or alkenyl succinic anhydride.

8. 8. A formulation according to any one of claims 1 to 7, wherein the hydrolysed protein comprises cross-links, the cross-linking agent being a diglycidyl ether or a triglycidyl ether, optionally alkoxylated.

9. 9. The formulation of 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. 10. The formulation of claim 8 or claim 9, wherein the cross-linking agent is selected from glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.

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

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

10. A concentrate formulation comprising:

13. 13. The concentrate formulation of claim 12, wherein the formulation is a suspension concentrate (SC) or a suspoemulsion (SE).

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

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

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