Biodegradable polyesters for use as dispersants and agricultural compositions comprising same

Abstract

The present invention provides a biodegradable polyester that can be used as a dispersant for agricultural formulations. In addition, the present invention further provides an agricultural composition comprising the same.

Description

[0001] This application claims priority from international procedure No. PCT / EP2022 / 072231 filed on August 8, 2022, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0002] The present invention provides a biodegradable polyester which can be used as a dispersant for agricultural formulations. In addition, the present invention further provides an agricultural composition comprising the same. Background Art

[0003] Agricultural compositions are becoming more and more complex, with high loads of active ingredients that are sparingly soluble or even insoluble in water, and / or combined systems combining said active ingredients with several modes of action with different physicochemical characteristics: for example, one active substance may be in the form of a soluble salt, while another active substance is dispersed in the aqueous phase.

[0004] Thus, agricultural compositions typically contain dispersants to improve dispersion, and in particular to provide uniformity and to help reduce and / or prevent flocculation and aggregation.

[0005] Dispersion is the process by which agglomerates of solid particles become separated and a new interface is formed between each smaller particle and the surrounding medium. This process is facilitated by the application of external forces (grinding) and the use of amphiphilic additives such as dispersants.

[0006] However, there is an increasing demand for readily biodegradable compounds in most fields today. This is also the case in the agrochemical field, where surfactants including dispersants with good environmental characteristics combined with good stability and efficacy of pesticides and fertilizers are being sought, and there will be a need to replace such non-biodegradable dispersants.

[0007] There are some biodegradable non-polymeric surfactants such as phosphate esters, but they are not very versatile for many active ingredients and there is a need to use polymeric dispersants in order to stabilize agricultural formulations. Lignin sulfonates and EO-PO are biodegradable and can be used as polymeric dispersants, however they are not versatile.

[0008] To date, there remains a desire to develop more versatile polymeric biodegradable dispersants, particularly for use in agricultural formulations. Summary of the invention

[0009] In one aspect of the present invention, there is provided a biodegradable polyester that can be used as a dispersant for agricultural formulations.

[0010] The biodegradable polyester can be prepared from a monomer composition comprising:

[0011] (a) a sulfonated dicarboxylic acid monomer (SA) selected from the group consisting of: at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof;

[0012] (b) a polyhydroxy polyol (P) selected from the group consisting of at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethylene oxide value in the range of 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units; and

[0013] (c) a dihydroxy compound (DH) selected from C5-C 10 Alicyclic diols, C5-C 10 Cycloaliphatic diacids, C2-C8 hydroxylated aliphatic acids, or combinations thereof.

[0014] The biodegradable polyester may comprise the following repeating units (I) and (II):

[0015]

[0016] wherein R1, R2, R3, and R4 are independently selected from H or C1-C8 alkyl;

[0017] A is selected from C5-C 10 an alicyclic group or an aromatic group; and

[0018] n and m are numbers in the range of 1 to 200.

[0019] In another aspect of the present invention, there is provided an agricultural composition comprising a pesticide and the biodegradable polyester of the present invention.

[0020] It has been noted that the agricultural composition according to the invention reduces, or even prevents, crystal growth of the dispersed agricultural material and also ensures good performance in terms of dilution, including good suspensibility of the agricultural material, even for high-load formulations.

[0021] The agricultural composition according to the present invention exhibits high storage stability over time.

[0022] It has also been noted that the agricultural composition according to the invention has a good viscosity and a good dispersion of the agricultural material, which allows an easier application to the soil, plants and / or seeds.

[0023] In still another aspect of the present invention, there is provided use of the biodegradable polyester of the present invention as a dispersant for an agricultural composition.

[0024] In yet another aspect of the present invention, there is provided use of an agricultural composition according to the present invention for treating soil, plants and / or seeds to control pests and / or regulate plant growth.

[0025] In yet another aspect of the present invention, there is provided a method for treating soil, plants and / or seeds to control pests and / or regulate plant growth by applying a composition according to the present invention to at least one plant, an area adjacent to a plant, soil suitable for supporting plant growth, roots of a plant, leaves of a plant, and / or seeds suitable for producing a plant. DETAILED DESCRIPTION

[0026] Throughout this specification, including the claims, unless otherwise indicated, the term "comprising one" or "comprising a" should be understood as being synonymous with the term "comprising at least one." The terms "between" and "from... to..." should be understood to include the limits.

[0027] Use of the articles "a," "an," and "the" means that the grammatical object of the article is one or more than one (ie, to at least one).

[0028] It should be noted that when any range of concentrations, weight ratios or amounts is indicated, any specific upper concentration limit, weight ratio or amount can be associated with any specific lower concentration limit, weight ratio or amount, respectively.

[0029] As used herein, the term "alkyl" means a saturated hydrocarbon group which may be linear, branched or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl.

[0030] As used herein, the term "(Cn-Cm)" with respect to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.

[0031] The suspensibility of an agricultural composition is defined as the weight percentage of one or more agricultural materials that remain in suspension after dilution of the composition in water (CIPAC A or D standard water) at a certain %wt (e.g. 1%wt in water) after a given time, relative to the total weight of the compound. The term "good suspensibility" is intended to mean a suspensibility of greater than or equal to 70%, in particular greater than or equal to 80%, more particularly greater than or equal to 85%, for example greater than or equal to 90%.

[0032] The suspensibility of the composition can be determined, for example, according to CIPAC method MT184.

[0033] The term "good storage stability" is intended to mean a composition that remains homogeneous over time (i.e. it exhibits substantially no or limited phase separation (sedimentation, syneresis, etc.)), in particular that remains substantially homogeneous when stored at 0°C for at least one week, at 54°C for at least 2 weeks or at 45°C for at least 3 months (CIPAC MT39.3 and MT 46.3 standardized tests).

[0034] The term "good viscosity" or "flowability" is intended to mean a composition that exhibits "good flowability", i.e. a composition with a suitable viscosity, for example a viscosity greater than 300 cP (i.e. 300 mPa.s) measured at 20 rpm and 25° C. using a Brookfield RV viscometer, in particular a viscosity greater than 300 cP (i.e. 300 mPa.s) and less than 10,000 cP (i.e. 10,000 mPa.s). In addition, a shear thinning curve is generally required, i.e. a decrease in viscosity when the shear rate increases, in order for the composition to have good flowability. The concentrated agricultural composition of the present invention must in particular remain pumpable.

[0035] The term "suitable dispersion" or "good dispersion" is intended to mean a dispersion after dilution in water (CIPAC A or D standard water) which is homogeneous over time (i.e. exhibits substantially no phase separation (sedimentation, syneresis, etc.)), in particular which remains substantially homogeneous when stored in a thermostatically controlled water bath at 30° C. for 30 minutes, preferably in a thermostatically controlled water bath at 30° C. for 2 hours and ideally in a thermostatically controlled water bath at 30° C. for 24 hours (modification of the CIPAC MT180 test). Such a dispersion must in particular be able to ensure good use properties of the dispersed compound.

[0036] Crystal growth by "Ostwald ripening" generally occurs when smaller crystals (which have a greater surface area than larger crystals) dissolve in the aqueous phase and the material is transported through the continuous phase to the nucleation sites of the larger crystals. As a result, crystals of agricultural materials may aggregate and settle, the composition becomes inhomogeneous; during application, filters and nozzles of spray equipment may become clogged and biological efficacy may be reduced.

[0037] The particle size D(50) and D(90) values ​​were determined by dynamic light scattering analysis using a Malvern Mastersizer 2000 with a Hydro2000SM accessory operating in deionized water. The particle size D(50) and D(90) values ​​correspond to particle diameters such that the cumulative undersized volume fraction of particles is equal to 50% and 90%, respectively. From the obtained particle size values, the D(50) and D(90) values ​​are readily determined.

[0038] The crystalline morphology of the material was evaluated by optical microscopic observation. The samples were diluted to 5% w / w solutions in deionized water, and images of the crystalline material were taken and processed. In some cases, arbitrary line measurements on the resulting images were used to confirm the particle size of the crystals.

[0039] Biodegradable polyester

[0040] In one aspect of the present invention, there is provided a biodegradable polyester for use as a dispersant for an agricultural composition. The biodegradable polyester can be prepared from a monomer composition comprising:

[0041] (a) a sulfonated dicarboxylic acid monomer (SA) selected from the group consisting of: at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof;

[0042] (b) a polyhydroxy polyol (P) selected from the group consisting of at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethylene oxide value in the range of 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units; and

[0043] (c) a dihydroxy compound (DH) selected from C5-C 10 Alicyclic diols, C5-C 10 Cycloaliphatic diacids, C2-C8 hydroxylated aliphatic acids, or combinations thereof.

[0044] The sulfonated dicarboxylic acid monomers (SA) have at least one sulfonic acid group, preferably in the form of an alkali metal or alkaline earth metal (preferably sodium) sulfonate, and two acidic functional groups or acidic functional group equivalents (i.e. an anhydride functional group or two ester functional groups), which are attached to one or more aromatic rings when it comes to aromatic dicarboxylic acids or anhydrides or diesters thereof, or to an aliphatic chain when it comes to aliphatic dicarboxylic acids or anhydrides or alkyl diesters thereof.

[0045] Among the sulfonated dicarboxylic acid monomers (SA), mention may be made of aromatic sulfonated dicarboxylic acids or anhydrides, such as sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydride, 4-sulfo-2,7-naphthalene dicarboxylic acid or anhydride, sulfo-4,4′-bis(hydroxycarbonyl)diphenyl sulfone, sulfodiphenyl dicarboxylic acid or anhydride, sulfo-4,4′-bis(hydroxycarbonyl)diphenylmethane, sulfo-5-phenoxyisophthalic acid or anhydride or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters, and sulfonated aliphatic sulfonated dicarboxylic acids or anhydrides, such as sulfosuccinic acid or anhydride or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters. In one embodiment of the present invention, the sulfonated dicarboxylic acid monomer (SA) is selected from aromatic sulfonated dicarboxylic acids, preferably sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydrides or lower diesters thereof.

[0046] The polyhydric polyol (P) used in the present invention is at least one polyol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethylene oxide value in the range of 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units; preferably ethylene glycol and / or glycerol are used.

[0047] The dihydroxy compound (DH) used in the present invention is selected from C5-C 10 Alicyclic diols, C5-C 10 Alicyclic diacid, C2-C8 hydroxylated aliphatic acid, or a combination thereof. 10 Illustrative examples of cycloaliphatic diols include, but are not limited to, cyclohexanedimethanol, and illustrative examples of C2-C8 hydroxylated aliphatic acids include, but are not limited to, glycolic acid, C5-C 10 Illustrative examples of cycloaliphatic diacid monomers include, but are not limited to, cyclohexanedicarboxylic acid.

[0048] In one embodiment of the present invention, more than one dihydroxy compound may be used, for example, cyclohexanedimethanol and cyclohexanedicarboxylic acid may be used together in the present invention.

[0049] In another embodiment of the present invention, one or more dihydroxy compounds are used in an amount of 0.1% to 50%, preferably between 0.5% to 25%, more preferably between 0.5% to 15%, based on 100 mol% of the biodegradable polyester.

[0050] In one embodiment of the present invention, the monomer composition for preparing the polyester further comprises:

[0051] (d) a diacid component, which is at least one selected from the group consisting of:

[0052] d1) an unsulfonated dicarboxylic acid monomer (A) consisting of at least one dicarboxylic acid or a derivative thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and furandicarboxylic acid; and

[0053] d2) Polyester prepolymers prepared from unsulfonated dicarboxylic acid monomers (A) or derivatives thereof and polyhydric polyols (P).

[0054] In one embodiment of the present invention, the unsulfonated dicarboxylic acid monomer (A) consists of isophthalic acid and / or furandicarboxylic acid.

[0055] In the unsulfonated dicarboxylic acid monomers (A), there may additionally be present small amounts of aromatic diacids other than those mentioned above, such as phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and biphenyl dicarboxylic acid, or aliphatic diacids, such as adipic acid, glutaric acid, succinic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, itaconic acid and maleic acid, etc., in the form of acids, anhydrides or lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.

[0056] The prepolymer c2) used in the present invention is prepared from unsulfonated dicarboxylic acid monomers, dicarboxylic acid monomers (A) or derivatives thereof and polyhydroxy polyols (P). In one embodiment of the present invention, the prepolymer c2) is polyethylene terephthalate, which can be prepared from terephthalic acid, isophthalic acid, ethylene glycol and / or diethylene glycol. Preferably, the prepolymer c2) has an intrinsic viscosity in the range of 0.1 to 0.9 dL / g as determined according to ASTM method D-4603, and has a maximum melting point of 250°C.

[0057] The biodegradable polyester used as a dispersant of the present invention can be prepared by esterification or transesterification and polycondensation according to common knowledge in the art. US 09 / 887664 discloses such a method for preparing water-dispersible polyester polymers, which is hereby incorporated herein by reference in its entirety.

[0058] In one embodiment of the present invention, the biodegradable polyester comprises the following repeating units (I) and (II):

[0059]

[0060] wherein R1, R2, R3, and R4 are independently selected from H or C1-C8 alkyl;

[0061] A is selected from C5-C 10 an alicyclic group or an aromatic group; and

[0062] n and m are numbers in the range of 1 to 200.

[0063] In one embodiment of the present invention, one of R1 and R2 is selected from H, and the other is selected from H, methyl, ethyl, propyl, or butyl, preferably methyl.

[0064] In one embodiment of the present invention, the biodegradable polyester further comprises repeating units (III)

[0065]

[0066] wherein R5 and R6 are independently selected from H or C1-C8 alkyl; and

[0067] p is a number in the range of 1 to 200.

[0068] In one embodiment of the present invention, one of R5 and R6 is selected from H, and the other is selected from H, methyl, ethyl, propyl, or butyl, preferably methyl.

[0069] In another embodiment of the present invention, the biodegradable polyester further comprises at least one of repeating units IV to VI,

[0070]

[0071] wherein A is as defined above, and B is selected from C5-C 10 Alicyclic group.

[0072] In one embodiment of the present invention, as presented in repeating units IV to VI, B represents a hexamethylene group.

[0073] In one embodiment of the present invention, as presented in repeating units II to V, A is selected from hexamethylene.

[0074] Agricultural preparations.

[0075] In another aspect of the present invention, there is provided an agricultural composition comprising:

[0076] (I) agricultural materials; and

[0077] (II) A biodegradable polyester as defined above.

[0078] The agricultural composition according to the present invention comprises at least one agricultural material.

[0079] As used herein, the term "agricultural material" means an active ingredient used in agricultural practices, including cultivating soil for crop growth. However, the use of agricultural materials is not limited to application to crops. Agricultural materials can be applied to any surface, such as for the purpose of cleaning or assisting or inhibiting the growth of living organisms. Other non-crop applications include, but are not limited to, application to animals, such as livestock, application to turf and ornamental plants, and application to railroad weeds.

[0080] Preferably, the one or more agricultural materials are selected from the group consisting of pesticides, biocides, nutrients, biostimulants, plant growth regulators, and mixtures thereof.

[0081] For example, pesticides include fungicides, herbicides, insecticides, algaecides, molluscicides, miticides, nematicides, and rodenticides.

[0082] For example, antimicrobial agents include antiseptics, antibiotics, antibacterial agents, antiviral agents, antifungal agents, antiprotozoal agents, and antiparasitic agents.

[0083] More preferably, the one or more agricultural materials are selected from the group consisting of fungicides, herbicides, insecticides, algaecides, molluscicides, miticides, nematicides, rodenticides, bactericides, antibiotics, antibacterial agents, antiviral agents, antifungals, antiprotozoal agents, antiparasitic agents, and mixtures thereof.

[0084] Suitable pesticides, biocides, plant growth regulators, nutrients and biostimulants for use in the compositions according to the invention may be chosen from those cited in the international application WO 2019 / 185851 from CRODA.

[0085] The term 'pesticide' is understood to refer to any substance or mixture of substances intended to prevent, destroy, drive or mitigate any harmful organism. Pesticides can be chemicals, biological agents (such as macroorganisms, microorganisms), chemical semiochemicals (such as pheromones) or natural substances of mineral, plant or animal origin for combating harmful organisms, including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms) and microorganisms, which compete with people for food, destroy property, spread diseases or cause nuisance. Pesticides include biological pesticides. The technician is familiar with such pesticides, which can be found, for example, in Pesticide Manual [pesticide manual], the 16th edition (2013), British Crop Protection Committee, London. In the following examples, pesticides suitable for use in agricultural compositions according to the present invention are given.

[0086] Preferably, according to the present invention, the pesticide is selected from the group consisting of insecticides, fungicides, herbicides, miticides, and mixtures thereof.

[0087] Fungicide refers to any substance or mixture of substances used to prevent the spread of fungi in gardens and crops. Fungicides are also used to combat fungal infections. Fungicides can be contact or systemic. Contact fungicides kill fungi when they come into contact with the fungicide, which remains on the surface of the leaves. Systemic fungicides are absorbed into plant tissues and kill the fungi when they try to invade the host.

[0088] Examples of fungicides that can be used in the present disclosure include, but are not limited to: (3-ethoxypropyl)-mercuric bromide, 2-methoxyethylmercuric chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercuric oxyquinoline, acibenzolar, acibenzolar-S-methyl, acypetacs, copper acypetacs, zinc acypetacs, aldimorph, allyl alcohol, pyraclostrobin, indazolesulfazoline, ampropylfos, dithiocarb, aureomycin, azaconazole, thiramoxydim, azoxystrobin, barium polysulfide, bensulfuron, bensulfuron-M, oxazolidinone, benomyl, benomyl, quinone oxime hydrazone, bentaluron, benthiastrobin, benthiastrobin isopropyl ester, Benzalkonium chloride, benzyl cyanamide acrylate, benzyl cyanamide acrylate isobutyl, antibacterial chloranil, benzohydroxamic acid, benzathiazolin, binacarb, biphenyl, triadimefon, thiochlorophenol, chloroflubifenazate, blasticidin-S, Bordeaux mixture, boscalid, oxadiazine, pyrimidine sulfonate, sodium carbonate Bordeaux mixture, butylthiocyanate, butylamine, calcium polysulfide, captamipan, captan, morphine, carbendazim, carboxin, cyproconazole, carvone, chelating agent mixture, mite-killing agent, thiocyanate, diamine, tetrachloroquine, benzyl imidazole, chlorodinitronaphthalene, chloroanisole, chloropicrin, thiophanate-methyl, tetrachloroquinoxaline, ethylthiocyanate, climbazole, clotrimazole, copper acetate, basic copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, silicic acid Copper, copper sulfate, copper zinc chromate, cresol, thiocarb, copper chloride, cuprous oxide, cyazolin, cyclamic acid, cyclohexanil, cyfluanid, cymoxanil, cyanamide, cyproconazole, cyproconazole, dazomethane, dazomethane sodium, DBCP, imidacloprid, tin decasulfuron, dehydroacetic acid, benzfluorosulfonamide, dichloronaphthoquinone, dichlorophenol, sclerotium, benzyltriazole, dichlorocyanamide, dacron, dacron sodium, chlornitril, ethochlor, diethyl pyrocarbonate, fenpropimorph, fluazifop, dimethomorph, dacron ... OC-potassium, DNOC-sodium, dodecacyclic morpholine, dodecacyclic morpholine acetate, dodecacyclic morpholine benzoate, polydioxanil, polydioxanil sodium, polydioxanil, hydrazine, dichlorvos, fluopicolide, ethiconazole, mancozeb, ethidium, thiabendazole, ethoxyquin, 2,3-dihydroxypropylsulfanylethylmercury, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, thiabendazole, oxadiazine, imidacloprid, sodium sulfamethoxam, imidacloprid, chlorfenapyr, fenbuconazole, furamide, fenhexamid, seed clothing ester, rice blastamide, fenpropathrin, fenpropidin, fenbutanil, triphenyltin, triphenyltin chloride, triphenyltin hydroxide, ferram, pyrimidine, fluazinam, fluoxonil, fluoxanil, flumorph, fluopicolide,Fluopyram, fluchlorfenapyr, triflubenazole, fluoxastrobin, fluquinconazole, flusilazole, sulfaquinamide, fluthiazolin, flutolanil, flutolanil, fluopyram, folpyroxanil, formaldehyde, phosphonic acid, phosphonate aluminum, wheat spike, furalaxyl, furazolidone, dimethylfuranamide, furconazole, cis-fuconazole, furfural, seed dressing amine, furothiocarb, fruit green pyridin, griseofulvin, biguanide, quinoline acrylate, hexachlorobenzene, hexachlorobutadiene, hexaconazole, cyclohexylthion, naphthalene sulfonic mercury, oxadipamide, imazalil, imazalil nitrate, imazalil sulfate, imipenem, biguanide, biguanide triacetate, biguanide trioctyl alkylbenzene sulfonate, iodomethane, oxadipamide, isoproconazole, valeric acid, rice blast, pyraclostrobin, isothiazolamide, chlorpyrifos, spring thunder Mycobacterium, kresoxim-methyl, mancozeb, mancozeb, mancozeb, maneb, o-amide, benzocarb, myclobutanil, oxadiazine, nitrobenzene, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl, 100 mu, 100 mu ammonium, 100 mu potassium, 100 mu sodium, cyclohexanone, metconazole, sulfamethoxam, furazolidone, methyl bromide, methyl isothiocyanate, methylmercury benzoate, cyanoguanidine methylmercury, pentachlorophenol methylmercury, mesamiprole, fenoxystrobin, mefenoxam, thiopyrad, mesamiprole, meclofenoxam, N-(ethylmercury)-p-toluene-sulfonylanilide, mancozeb, natamycin, nitrostyrene, phthalostrobin, fluphenazine, OCH, octhilthione, furamide, oxadiazine, oxadiazine, quinoline copper, oximidazole, oximidazole fumarate, oxycarboxin, rice blast ester, Penconazole, pencuron, fluopicolide, pentachlorophenol, penthiopyrad, phenylmercury urea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivatives of catechol, phenylmercury nitrate, phenylmercury salicylate, chlorpyrifos, tetrachlorophthalide, picoxystrobin, pyraclostrobin, mancozeb, polyoxins, polyoxorim, polyoxorim zinc, potassium azide, potassium polysulfide, potassium thiocyanate, allylbenzazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propoxyquin, thiocarb, thiocarb hydrochloride, prothioconazole, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin , chlorpyrifos, quinacridone, quinacridone sulfate, quinazoline, quinoxaline, phenoxyquinoline, pentachloronitrobenzene, pyrimidine, salicylaniline, fluazole cyclamic acid, silthiopyrad, siloxane, sodium azide, sodium o-phenylphenol, sodium pentachlorophenol, sodium polysulfide, spiroxane, streptomycin, sulfur, pentamethylene sulfone, TCMTB, tebuconazole, isobutyl ethoxyquinoline, chlorothiazide, tetrachloronitrobenzene, fordiosulfur, tetrafluthrin, thiabendazole, thiadiazole, thiadiazole, thiabend ...Tricyclazole, tridemorph, trifloxystrobin, triflumizole, trifloxystrobin, trichlorfon, chloranil, chloranil, chloranil, cypermethrin, valerian, vinclozolin, cyanamide, zinc cyclohexane, mancozeb, ziram, zoxanil and mixtures thereof.

[0089] Herbicides are pesticides used to kill unwanted plants. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these work by interfering with the growth of weeds and are usually based on plant hormones. Herbicides used to clear wasteland are non-selective and kill all plant material that comes in contact with them. Herbicides are widely used in agriculture and landscape turf management. They are applied to total vegetation control (TVC) projects for highway and rail maintenance. Small amounts are used in forestry, pasture systems, and the management of areas reserved for wildlife habitat.

[0090] Examples of herbicides that can be used in the present disclosure include, but are not limited to, 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, bennitropropane, acrolein, alachlor, dimethoate, chlorfenapyr, allyl alcohol, pentachloropentane, terzinone, ametryn, terbazone, aminopyralid, acylamidosulfuron, chlorpromazine, chloranil, methylamine, chlorfenapyr, ammonium sulfamate, cypermethrin, sulfamic acid, chloranil ... CPC, fluazifop, chloranil acid, benzathinesulfuron, ethyl fluazifop, furosulfuron, benzylsulfuron acid, dithionite, bentazon, amine acid, bispyribac, benzylpyridin, bicyclam, pyraclostrobin, benzofiuor, neocarbamic acid, benzylpyridin, fluazifop, carboxylic acid butyl, bialaphos acid, bispyribac-butyl, borax, herbicide, furanil, bromobutyric acid, bromophenol oxime, bromoxynil, bromomycin, butachlor, fluazifop-butyl, chloranil, butachlor ... EPC, methoxy-nitroprop-butyl, chlorfenapyr, butyralid, chlorfenapyr, colazine, chlorbromid, chlorfenapyr, ethoxysulfuron, famoxadone, oat acid, fluguanil, chlorhydroxyfluoric acid, chlorfenapyr, chlorsulfuron, chlorsulfuron acid, chlorfenapyr, trichloropropionic acid, chlorotoluron, chlorfenapyr, hydroxydichloraniluon, chlorpropamide, chlorsulfuron, chlorthalid, chlorsulfuron, indolone, cyproconazole, ethersulfuron, chlorfenapyr , clethodim, iodine chlorpyrifos, clodinafop-butyl, propionic acid, clomazone, chloranil, fruit acid, cyclohexene chlorpyrifos, clopyralid, clorac, CMA, copper sulfate, CPMF, CPPC, ether grass amine, mixed methylphenol, diphenyl sulfamethoxam, cyanamide, cyanazine, cyclohexane, cyprosulfuron, cyprosulfuron, cyprosulfuron, cyprosulfuron, cyprosulfuron, cyprosulfuron acid, cyprosulfuron ... Thiazole, cypermethrin, dimethoate, dazomethon, isobutachlor, betaine, dichlorprop, avena citrate, dicamba, dichlornitrile, chloranil, dichlorprop, dichlorprop-P, chloranil acid, bispyribac, diethyl chlorpyrifos, acetophenone, flufenac, cypermethrin, dichlorprop, dichlorprop-P, oxazolidinone, fluazifop, flufenac, fluazifop, flufenac, fluazifop, oxazolidinone, flufenac, dimethoate, isopentyl, dimethoate ...DNOC, DSMA, EBEP, grass stop, endorphin, triazole sulfone, EPTC, grass styrene, pentocarb, ethosulfuron, sulfothiocarb, ethoxyfuran, fluroxypyr, ethosulfuron, nitrosamine, ethosulfuron, ethosulfuron, EXD, acetosulfuron, 2,4,5-fenopropic acid (fenoprop), oxadiazine acid, fenoxaprop-P, benzylpyridinium chloride, trichlorophenoxyethanol, thiamethoxam acid, tetrazolylpyridinium chloride, fenomenon, ferrous sulfate, wheat grass fluoride, refined wheat grass fluoride, fluazifop-butyl, bispyribac, fluazifop-butyl acid, refined fluazifop-butyl acid, isopropylpyridinium chloride, fluazifop-butyl, fluazifop-butyl, chlorpyrifos, flufenacet, flufenacet, Flupyridazine oxalic acid, fluazifop, trifluoxazine, flufenoxac, fluazifop, flufenoxac, fluazifop, chloranil, fluazifop, trifluanid, fluazifop acid, chloranil, flunifen, fluthiocarb, flufenoxam, tetrafluoropropionic acid, fluazifop, flufenoxam, fluazifop, flufenoxam, flusulfuron, fluazifop, flufenoxam, fluazifop, flufenoxam, fluamidosulfuron, fluazifop, fluazifop, flumioxam ... Iodomethane, methyl iodosulfuron acid, iobenzonitrile, oxazolidinone, triazole, acetamidopyr, imidopropyramide, isothiocarb, butyric acid, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, isothiocarb, terbuconazole, ketospiradox, lactofen, cypermethrin, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, 2,4-dichloropropionic acid, 2,4-dichloropropionic acid, nitrophenol, mefenacet, flusulfamide, methamphetamine, disulfuron acid, mesotrione, metamidine, oxadiazine, metamefenacet, pyraclostrobin, fluazifop, methylbenzenesulfuron 、Flufenpyroxil, chlorpyrifos, methiobencarb, chlorpyrifos, methoxyfen, methyl bromide, methyl isothiocyanate, methyl chlorpyrifos, pyranol, bromothiocarb, isopropyl chlorpyrifos, sulfamethoxazole, methomyl, methomyl, methomyl, chlorpyrifos, monochloroacetic acid, chlorpyrifos, chlorpyrifos, chlorpyrifos, MSMA, naphthamide, propamide, naphthamide, chlorpyrifos, nicosulfuron, fluchloramine, sulfol, herbicide, trifluoroacetate, fluazifop, chlorpyrifos, OCH, pyrochloran, o-dichlorobenzene, pyrimidine sulfone, amoxicillin, oxadiazine, oxadiazine, oxadiazine, oxadiazine, parafluoron, paraquat, chlorpyrifos, nonanoic acid, pendimethalin,Penoxsulam, pentachlorophenol, meclofenamide, cypermethrin, fluazifop, pethodiamide, cotton amine, betaine, betaine ethyl ester, acylam, phenylmercuric acetate, ampicillin, fluazifop, pinoxaden, pyralid, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, cyprosulfuron acid, cyproconazole, ammonia fluazifop, fluazifop, cyprosulfuron, cyproconazole, cyproconazole, pyralid, fluazifop, cyprosulfuron, cyproconazole, pyralid, fluazifop, cyprosulfuron, cyproconazole, pyralid, fluazifop, cyprosulfuron, cyprosulfuron, cyprosulfuron, pyralid, fluazifop, cyprosulfuron, cyprosulfuron, pyralid, fluazifop, cyprosulfuron, pyralid, fluazifop, cyprosulfuron, pyralid, fluazifop, cyprosulfuron, pyralid Azamisulfuron-methyl, propyzamide, methylsulfuron, bensulfuron, prosulfuron, propyzamide, propyzamide, bidanone, bifenthrin, pyraclostrobin acid, pyraclostrobin, pyrazosulfuron acid, bensulfuron, pyraclostrobin, barnyardgrass, chlorpyrifos, chlorpyrifos, chlorpyrifos, pyraclostrobin, pyraclostrobin acid, pyraclostrobin, sulfamethoxam, sulfamethoxam, sulfamethoxam, sulfamethoxam, sulfamethoxam, sulfamethoxam, quinclorac acid, chlormequat, chloranil, chloranil, chloranil, quinclorac acid, chlormequat, chloranil, quinclorac acid ... Amine, S-isopropyl metolachlor, another butylazine, sec-butyltong, sethoxydim, cypermethrin, simazine, simathon, simethoxam, SMA, sodium arsenite, sodium azide, sodium chlorate, sulfothiocarb, chloranil, sulfentrazone, sulfentrazone, sulfosulfuron, sulfosulfuron, sulfuric acid, azoxystrobin, mefenamic acid, TCA, oxadiazine, butylthiocarb, furazolidinone, cypermethrin, pyraclostrobin, terbuconazole ... on), thiazolin, thiadiazole, thiadiazole, thiadiazole, thiamethoxam, thiamethoxam, thiamethoxam acid, fenthiocarb, fenthiocarb, pyraclostrobin, wild wheat, ether bensulfuron, triazinon, bensulfuron acid, chlorpyrifos, triclopyr, chloranil, thiocarb, trifloxysulfuron, fluralin, flufenacil, trifloxysulfuron acid, trifloxysulfuron acid, trifloxysulfuron oxime, cyanuric acid, isothiocarb, trifloxysulfuron, vemolate, dimethoate and mixtures thereof.

[0091] Safener means an active ingredient applied with a herbicide to protect crops from injury. Some safeners that may be used in the present disclosure include, but are not limited to, fenthiocarb, fenthiocarb, fenthiocarb-butyl (quinoline-mexyl), fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, fenthiocarb-butyl, MG 191, MON 4660, naphthalene anhydride (NA), fenthiocarb-butyl, R29148, N-phenylsulfonylbenzoic acid amide and mixtures thereof.

[0092] Insecticides are pesticides used against all developmental forms of insects and include ovicides and larvicides used against insect eggs and larvae. Insecticides are used in agriculture, medicine, industry and in the home.

[0093] Examples of insecticides that can be used in the present disclosure include, but are not limited to: 1,2-dichloropropane, avermectin, acetamiprid, acetamiprid, domesticaphos, acetothion, flumethrin, acrylonitrile, cotton boll carb, aldicarb, aldicarb, aldrin, ylenin, aloamicin, cypermethrin, α-cypermethrin, α-ecdysone, α-endosulfan, cypermethrin, cypermethrin, amiphos, amiphos oxalate, amitraz, neonicotinoids, ethyl methidathion, azadirachtin, methyl pyraclostrobin, ethyl azinphos-methyl, methyl azinphos-methyl, azophos, barium hexafluorosilicate, caprylin, benfuracarb, benfuracarb, sulfamethoxam, high-efficiency cypermethrin, high-efficiency cypermethrin, bifenthrin, bio-allethrin, bio-methyl acetate, bio-permethrin, bistridine ifluoron), borax, boric acid, bromophenazone, bromocyclohexene, bromo-DDT, bromophos, ethyl bromophos, butylbenzenecarb, buprofezin, cypermethrin, demethyl butylpyrimidin, butanone, butolate, butanone oxycarb, cadusin, calcium arsenate, calcium polysulfide, toxaphene, chlormethoxam, carbaryl, furadan, carbon disulfide, carbon tetrachloride, trithion, butanthracene, carbofuran, carbofuran hydrochloride, chlorfenapyr, bornyl carbendazim, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chloroxyphos, chlorfenapyr, chlorfenapyr, chlorfenapyr, chloromethylphos, chloroform, chloropicrin, chlorphophos, chlorpyrifos, methyl chlorpyrifos, chlorfenapyr ... Taier, dinotefuran, copper acetylarensite, copper arsenate, copper cyclohexane, copper oleate, Kumarphos, cyclothion, crotamiton, butenphos, clofosinate, cryolite, benzonitrile, cypermethrin, fruit insect phosphorus, cyantraniliprole, cypermethrin, cypermethrin, cyhalothrin, cypermethrin, cypermethrin, cyproconazole, cymethrin, DDT, monomethyl carbofuran, cypermethrin, tianlephos, tianlephos-O, tianlephos-S, endophos, endophos-methyl, endophos-O, endophos-O-methyl, endophos-S, endophos-S-methyl, endophos-S-methanesulfonic acid, chlorpyrifos, chlorpyrifos, diatomaceous earth, diazinon, isochlorothion, dimethoate, dichlorvos, dimethoate, dicrotophos, dichlorvos, dimethoate, dimethoate, dimethoate, dieldrin, fenfluramide, dihydroxy Prophylline, tetrafluthrin, dimethoate, demicarb, dimethoate, pyrethrin, methyl chlorpyrifos, dichlorvos, chlorpyrifos, chlorpyrifos dicyclohexylamine salt, propanol, pentophenol, clothianidin, benzyl chlorpyrifos, vegetable phosphorus, dioxocarb, dimethoate, disulfothion, thiopyraphos, right-rotating limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysone, emamectin, emamectin benzoate, EMPC, empenfhrin, endosulfan, endrin, EPN, pyrifos, esdepallethrine, esdepallethrine, cypermethrin, ethosulf, ethophos, ethosulf, ethyl formate,Ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, ethomethrin, oxamethoxam, EXD, sulfamethoxam, fenamiphos, cypermethrin, fenitrothion, fenbutylcarb, oxamethoxam, fenoxycarb, cypermethrin, cypermethrin, fenthiocarb, fenthiocarb, ethyl fenthion, cypermethrin, flubendiamide, flufenoxam, flufenoxam, flufenoxuron, flucythrin, flumethrin, flufenoxuron, flufenoxuron, flufenoxuron Phosphate, famiparanate, famiparanate hydrochloride, anthiophos, fomiparanate, fomiparanate hydrochloride, butylfenthion, methyl chlorpyrifos oxide (fospirate), butylthiophos, furanfenozide, furathiocarb, furathiocarb, γ-cyhalothrin, γ-HCH, bromofluthrin, chlorfenapyr, HCH, HEOD, heptachlor, heptylphos, cypermethrin, hexaflumuron, HHDN, hydrazone, hydrogen cyanide, methoprene, quinoline, imidacloprid, imiprolin, indoxacarb, methyl iodide 、IPSP、chlorfenapyr、carbon chlorine、isocarb、isothion、isothion、methyl isofenphos、isoprocarb、rhizolamide、isoprofos、isoxazolin、ivermectin、jasmonate I、jasmonate II、iodine thiophos、juvenile hormone I、juvenile hormone II、juvenile hormone III、chlorpentyl、methoxyfen、λ-cyhalothrin、lead arsenate、lepidomectin、parabromophos、lindane、acetamiprid、lufenuron、isothion、malathion、propionyl cyanamide、azidophos、aphidazole、methyl aphidazole、aphidazole、chlorfenapyr、dithiocarb、 Phosphorus, mercurous chloride, fenthion sulfoxide, metaflumizone, acaricide, methamidophos, methidathion, methiocarb, monocrotophos, methoprene, methylthiothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methyl chloroform, methylene chloride, metofluthrin, metocarb, saliva chloranone, metochlor, milbemycin, milbemycin oxime, propylamine fluoride, ant killer, molosultap, monocrotophos, monomehypo, mono sultap), chlorpyrifos, moxidectin, naphthion, dibromophos, naphthalene, nicotine, niflumic acid, methoprene, nithiazine, nitrile, bisfluanid, polyfluanid, omethoate, oxamyl, sulfoxide, isosulfoxide, sulfone, p-dichlorobenzene, parathion, methyl parathion, fluoroquinolone, pentachlorophenol, permethrin, fenthion, phenoxythion, fenthion, fenthion, fenthion, chlorpyrifos, chlorpyrifos, phosphine ... Sulfur, methyl phoxim, methamidophos, pirimicarb, ethyl pirimiphos, methyl pirimiphos, potassium hydrogen arsenite, potassium thiocyanate, pp'-DDT, dextromethorphate, precocious ene I, precocious ene II, precocious ene III, acetyl pirimiphos, profenofos, cyprofluanid, profluthrin, fluthrin, cyprodinil, fenthrin, propanil, propanil, amine propanil, propoxur, ethidium thiophanate, prothiophos, fluthiophanate, fluphenazine, pymetrozine, pyraclostrobin, pyrazophos, pyrazophos, pyrafluanid, cyprodinil,Furan pyrethrin, pyrethrin I, pyrethrin II, pyrethrin, pyridaben, pyridalyl, pyridazinon, pyriflufen, pyrimidine, pyrimidine, pyrimidine, pyrimidine, pyrimidine, pyrimidine, pyrimidine, pyrimidine, quassia, quinalphos, methyl quinalphos, fenphos, rafoxanide, resmethrin, rotenone, ryanodine, veratridine, octamethylphos, selamectin, silafenthrin, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, thionylthion, ethyl spinosad, spinosad, spiromesifen, spirotetramat, sulfinamide, sulfinamide sodium, sulfluramid, sulfoxaflor, sulfuryl fluoride, sulfamethoxam, fluvalinate, thiamethoxam, TDE, cypermethrin, cypermethrin, pyrimidine, pyrimidine 、Fenfenamide, tefluthrin, temetofos, TEPP, cyclopentylthrin, tert-butylphos, tetrachloroethane, cypermethrin, tetramethrin, tetrafluthrin, θ-cypermethrin, thiamethoxam, thiochloridone, cypermethrin, cypermethrin, oxalate, thiodicarb, long-acting carb, dimethylthiocarb, cypermethrin, sulfamethoxam, thiodicarb, thio ...

[0094] Acaricides are pesticides that kill mites. Antibiotic acaricides, carbamate acaricides, formamidine acaricides, mite growth regulators, organochlorines, permethrins, and organophosphate acaricides belong to this category.

[0095] Molluscicides are pesticides used to control molluscs such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminum sulfate.

[0096] A nematicide is a chemical pesticide used to kill parasitic nematodes (helminths).

[0097] Preferably, the amount of the one or more pesticides in the composition ranges from 1% to 95% by weight relative to the total weight of the composition.

[0098] Preferably, the amount of the one or more antimicrobial agents in the composition ranges from 1% to 95% by weight relative to the total weight of the composition.

[0099] Preferably, the sum of the amount of the one or more antimicrobial agents and the amount of the one or more pesticides in the composition ranges from 1% to 95% by weight relative to the total weight of the composition.

[0100] The compositions according to the invention may comprise at least one biopesticide.

[0101] According to the present invention, the term "biopesticide" includes pest controlling microorganisms (microbial pesticides), pest controlling macroorganisms, pest controlling semiochemicals and pest controlling natural substances of mineral, plant or animal origin.

[0102] Microbial pesticides mean any microorganism, whether in a vegetative state, a dormant state (e.g., spores), or a whole broth culture, any substance derived from a microorganism (e.g., a metabolite), or any fermentation product (e.g., a supernatant, a filtrate, an extract, etc.), which is pathogenic to pests (e.g., capable of attacking, infecting, killing, crippling, causing disease, competing with pests, and / or causing damage to pests), and thus capable of being used to control pests by adversely affecting the viability or growth of target pests. Non-limiting examples of "microbial pesticides" include microbial nematicides, microbial insecticides, microbial fungicides, microbial bactericides, and microbial viricides).

[0103] Preferably, the biopesticide is selected from fungal spores and / or bacterial spores.

[0104] Examples of insecticidal or nematicidal or fungicidal fungal spores or conidia include, but are not limited to, the following classes: Basidiomycetes, Chytridiomycetes, Deuteromycetes, Hyphochytridiomycetes, Oomycetes, Plasmodiophoromycetes, Sordahomycetes, Thchomycetes and Zygomycetes, in particular the following fungi: Arthrobotrys superba, Arthrobotrys irregular, Beauveria bassiana, Erynieneoaphidis, Fusarium spp., Hirsute / Iarhossiliensis, Hirsutella thompsonii), Lagenidium giganteum, Metarhizium anisopliae, Myrothecium, Neozygietes fresenii (Nowakowski), Nomuraea rileyi, Paecilomyces lilacinus, Pseudomonas chloroaphis, Pseudomonas spp., Psedozyma Flocculosa, Trichoderma harzianum, and Vericillium lecanii., Verticillium lecanii, plus those endoparasitic fungi described in the book "Nematology Advances and Perspectives, Vol. 2 (2004), which is incorporated herein by reference in its relevant parts. Also included are fungal genera such as "Esteya vermicola" as described in U.S. Pat. No. 6,168,947 (incorporated by reference), and "Arkansas Fungus 18" as described in U.S. Pat. No. 5,019,389 (incorporated herein by reference).

[0105] Examples of bacterial spores include, but are not limited to, Bacillus agri, Bacillus aizawai, Bacillus albolactis, Bacillus amyloliquefaciens, Bacillus cereus, Bacillus circulans, Bacillus coagulans, Bacillus endoparasiticus, Bacillus endorhythmos, Bacillus firmus, Bacillus kurstaki, Bacillus lacticola, Bacillus lactimorbus, Bacillus lactis, Bacillus laterosporus, Bacillus lentus, Bacillus spores ... lentimorbus), Bacilluslicheniformis, Bacillus macerans, Bacillusmegaterium, Bacillus medusa, Bacillus metiens, Bacillus natto, Bacillus nigricans, Bacillus popillae, Bacilluspumiliss, Bacillus pumilus, Bacillus siamensis, Bacillus sphaehcus, Bacillus spp., Bacillussubtilis, Bacillusthuringiensis, Bacillusuniflagellatus, plus those in Todar's Online Textbook of Those listed in the Bacillus genus category in "Bacteriology [Todar's online textbook of bacteriology], (2009)", which is incorporated herein by reference in its relevant parts.Also included are Photorhabdus luminescens, Xenorhabdus nematophilus, Pantoea agglomerans, and those nematicidal bacterial antagonists listed in "Nematology Advances and Perspectives," Vol. 2 (2004).

[0106] Preferably, the amount of the one or more biopesticides in the composition ranges from 1% to 95% by weight relative to the total weight of the composition.

[0107] The composition according to the invention may comprise at least one nutrient.

[0108] Nutrients are chemical elements and compounds that are desirable or necessary to promote or improve plant growth. Nutrients are often described as either macronutrients or micronutrients.

[0109] Suitable nutrients for use in the composition according to the present invention may be micronutrient compounds, preferably those that are solid or partially soluble at room temperature (25°C).

[0110] Micronutrients typically refer to trace metals or trace elements, and are usually administered in lower doses. Suitable micronutrients include trace elements selected from zinc, boron, chlorine, copper, iron, molybdenum and manganese.

[0111] The micronutrients may be in soluble form or 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.

[0112] Preferably, the micronutrient may be chosen from zinc, calcium, molybdenum or manganese, or magnesium. More preferably, the micronutrient used in the composition according to the invention may be chosen from zinc oxide, manganese carbonate, manganese oxide, or calcium carbonate.

[0113] The composition according to the invention may also comprise at least one macronutrient.

[0114] Macronutrients typically refer to those containing nitrogen, phosphorus, and potassium, and include fertilizers such as ammonium sulfate and water conditioners. Suitable macronutrients include fertilizers and other nitrogen, phosphorus, or sulfur containing compounds and water conditioners.

[0115] Suitable fertilizers include inorganic fertilizers that provide nutrients such as nitrogen, phosphorus, potassium or sulfur. Examples of such fertilizers include:

[0116] - for nitrogen as a nutrient: nitrates and / or ammonium salts, such as ammonium nitrate, including in combination with urea, for example as uran-type materials, 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;

[0117] - for phosphorus as a nutrient: acidic forms of phosphorus, such as phosphoric acid, pyrophosphoric acid or polyphosphoric acid, but more usually in the form of salts, such as ammonium phosphates (especially monoammonium phosphate, diammonium phosphate and ammonium polyphosphate), potassium phosphates (especially potassium dihydrogen phosphate and potassium polyphosphate);

[0118] - For sulfur as a nutrient: ammonium sulfate and potassium sulfate, for example mixed with magnesium sulfate.

[0119] Preferably, the amount of the one or more nutrients in the composition ranges from 1% to 40% by weight, more preferably from 10% to 35% by weight, even more preferably from 15% to 30% by weight, relative to the total weight of the composition.

[0120] Preferably, the amount of the one or more micronutrients in the composition ranges from 1% to 40% by weight, more preferably from 10% to 35% by weight, even more preferably from 15% to 30% by weight, relative to the total weight of the composition.

[0121] Preferably, the amount of the one or more macronutrients in the composition ranges from 1% to 40% by weight, more preferably from 10% to 35% by weight, even more preferably from 15% to 30% by weight, relative to the total weight of the composition.

[0122] The term "biostimulant" is intended to mean a compound that can enhance a metabolic or physiological process such as respiration, photosynthesis, nucleic acid uptake, ion uptake, nutrient delivery, or a combination thereof.

[0123] Non-limiting examples of biostimulants include seaweed extracts (eg, ascophyllum nodosum), humic acid (eg, potassium humate), fulvic acid, inositol, glycine, and combinations thereof.

[0124] Preferably, the amount of the one or more biostimulants in the composition ranges from 0.001% to 10% by weight, more preferably from 0.01% to 5% by weight, even more preferably from 0.1% to 1% by weight relative to the total weight of the composition.

[0125] The compositions according to the invention may comprise at least one plant growth regulator.

[0126] Plant growth regulators refer to active ingredients used to affect the growth characteristics of plants. Examples of plant growth regulators that can be used in the present disclosure include, but are not limited to: 1-naphthylacetic acid, 1-naphthylacetic acid-salt, 1-naphthol, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, 2,4-DEP, 2,3,5-triiodobenzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2-naphthoxyacetic acid, 2-naphthoxyacetic acid sodium salt, 3-chloro-4-hydroxyphenylacetic acid, 3-indoleacetic acid, 4-biphenylacetic acid, 4-chlorophenoxyacetic acid (4-CPA), 4-hydroxyphenylacetic acid, 6-benzylaminopurine, auxin, α-naphthylacetic acid K-salt, β-naphthoxyacetic acid, p-chlorophenoxyacetic acid, dicamba, 2,4-dichlorprop, 2,4,5-fenoprop, indole-3-acetic acid (IAA), Indole-3-acetyl-DL-aspartic acid, indole-3-acetyl-DL-tryptophan, indole-3-acetyl-L-alanine, indole-3-acetyl-L-valine, indole-3-butyric acid (IBA), indole-3-butyric acid K-salt, indole-3-propionic acid; α-naphthylacetic acid, indole-3-acetic acid methyl ester, naphthylacetamide, naphthylacetic acid (NAA), phenylacetic acid, picloram, potassium cyclohexaneate, sodium cyclohexaneate, 4-hydroxyphenylethanol, 4-CPPU, 6-benzylaminopurine (BA), 6-(Y,Y-dimethylallylamino)purine (2iP), 2-iP-2HC1, adenine, adenine hemisulfate, benzyl adenine, kinetin, cytokinin (meta-topolin), N6-benzoyl adenine, N-benzyl-9-(2-tetrahydropyranyl) adenine (BP A), N-(2-chloro-4-pyridyl)-N-phenylurea, gibberellic acid (GA3), gibberellin, gibberellin A4+A7 (GA n), ethylene and abscisic acid.

[0127] Preferably, the amount of one or more plant growth regulators in the composition ranges from 1% to 95% by weight relative to the total weight of the composition.

[0128] Preferably, the agricultural composition according to the present invention is aqueous.

[0129] More preferably, the water content of the composition ranges from 5% to 99% by weight, more preferably from 20% to 98% by weight, even more preferably from 25% to 97% by weight relative to the total weight of the composition.

[0130] Preferably, the pH range of the agricultural composition is from 1 to 11; more preferably from 3 to 9; and even better from 4 to 8.

[0131] The pH of the agricultural composition can be adjusted to the desired value with the aid of an alkalizing agent or an acidifying agent. Among the alkalizing agents, one or more alkalizing agents can be used, such as ammonia, sodium hydroxide or ethanolamine. For example, among the acidifying agents, mention can be made of inorganic or organic acids, such as hydrochloric acid or orthophosphoric acid.

[0132] The agricultural composition according to the present invention may further contain additives different from the previously described ingredients, such as binders, diluents, absorbents, dispersants different from those previously described, carriers, disintegrants, wetting agents, emulsifiers, defoamers, antifreeze agents, solvents, viscosity regulators, preservatives and / or antimicrobial agents.

[0133] Mention may be made, for example, of (C1-C8)monohydric alcohols, (C2-C8)polyhydric alcohols, and mixtures thereof; such as ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof.

[0134] Each additive may be present in the agricultural composition according to the present invention in an amount ranging from 0% to 20% by weight, more preferably from 0% to 10% by weight, relative to the total weight of the composition.

[0135] A person skilled in the art will be able to select these optional additives and their amounts so that they do not impair the properties of the agricultural composition of the present invention.

[0136] Preferably, the viscosity is measured using a Brookfield RV viscometer at 25°C and atmospheric pressure (1.013×10 5 The viscosity of the aqueous agricultural composition according to the present invention measured at 20 rpm in an 80% saturation pressure ranges from 500 mPa.s to 1 500 mPa.s; more preferably from 700 to 1 300 mPa.s.

[0137] The agricultural composition according to the invention may be in the form of a concentrate, a diluted concentrate, or a sprayable dilution of one or more agricultural materials. In particular, the agricultural composition according to the invention may be in the form of an emulsifiable concentrate (EC), an emulsion in water concentrate (EW), a suspension concentrate (SC), a capsule suspension (CS), a ZC formulation, a flowable concentrate for seed treatment (FS), a water dispersible granule (WDG) and / or a suspoemulsion (SE).

[0138] More preferably, the agricultural composition according to the present invention is formulated as a suspension concentrate (SC), a flowable concentrate (FS) for seed treatment or a suspoemulsion (SE).

[0139] According to a preferred embodiment of the present invention, the agricultural composition is an aqueous suspension of one or more agricultural materials having a concentration greater than 0.05 g / L.

[0140] More preferably, according to this embodiment, the agricultural composition is an aqueous suspension of one or more agricultural materials having a concentration between 0.05 g / L and 1 200 g / L.

[0141] According to another preferred embodiment of the present invention, the agricultural composition is a concentrated aqueous suspension of one or more agricultural materials having a concentration greater than 50 g / L.

[0142] More preferably, according to this embodiment, the agricultural composition is a concentrated aqueous suspension of one or more agricultural materials having a concentration between 50 g / L and 1 200 g / L, even more preferably between 400 g / L and 1 200 g / L, for example above 700 g / L.

[0143] According to another preferred embodiment of the present invention, the concentrated agricultural composition can be diluted in water for use to obtain a diluted composition having a concentration of one or more agricultural materials greater than 0.05 g / L.

[0144] More preferably, according to this embodiment, the concentrated agricultural composition can be diluted in water for use to obtain a diluted composition having a concentration of one or more agricultural materials between 0.05 g / L and 120 g / L, even more preferably between 0.4 g / L and 120 g / L, for example above 0.7 g / L.

[0145] The copolymers according to the invention can also reduce the viscosity of the agricultural composition during grinding of the composition, compared to the viscosity of the same agricultural composition during grinding to which no copolymer according to the invention has been added.

[0146] Furthermore, the copolymers according to the invention may also reduce the temperature of the agricultural composition during grinding compared to the temperature of the same agricultural composition during grinding without the addition of the copolymers according to the invention.

[0147] Wet grinding is a method for preparing suspension concentrate formulations. The copolymer layer formed on the particles by the copolymer according to the invention can reduce / reduce the interaction between the particles, thereby reducing the viscosity and allowing the suspension to be loaded with high concentrations of particles without increasing the temperature of the system.

[0148] The inventive copolymers according to the invention therefore allow a greater density of the formulations and an efficient low-temperature wet grinding process.

[0149] According to a particular embodiment of the present invention, the agricultural composition according to the present invention is formulated as water dispersible granules (WDG).

[0150] The granules may include a solid carrier, filler or one or more diluent materials which are desirably inert to the one or more agricultural materials but readily dispersed in water, if necessary in combination with a dispersant. These materials may also have the benefit of reducing the dry mass and disintegration rate of the granules when added to water, and may also be used to adjust the concentration of the one or more agricultural materials.

[0151] Examples include clays, such as kaolin (china clay) and bentonite, which may be natural bentonite or modified (e.g. activated) bentonite, synthetic diatomaceous earth and diatomaceous earth, calcium and magnesium silicates, titanium dioxide, aluminum carbonate, calcium or magnesium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate or barium sulfate, charcoal, starch (including modified starches such as alkyl and carboxyalkyl starches), cellulose (such as microcrystalline cellulose), and cellulose derivatives (such as carboxyalkyl cellulose), and mixtures of two or more such solid carrier, filler, diluent materials.

[0152] The copolymer according to the present invention promotes the disintegration of particles after adding water to form a uniform dispersion, and ensures good performance when diluted, including good suspension of active ingredients, and causes low residues when the diluted formulation is passed through a 200 mesh size sieve. After dilution with 0.5% or 1.0% in CIPAC standard water A, D or C, the suspension performance can be evaluated with CIPAC method MT184. In the present application, after dilution with 1.0% in CIPAC standard water C, the suspension performance is evaluated with CIPAC method MT184. After dilution with 1% in CIPAC standard water D in a measuring cylinder, the ease of particle disintegration to form a dispersion is evaluated. The number of inversions of the measuring cylinder that completely disintegrates the particles and forms a suspension is evaluated, and the acceptance criterion is less than 30 inversions. In addition, the copolymer according to the present invention significantly reduces the amount of non-dispersible material obtained after dilution of the WDG formulation. The amount of non-dispersible material can be evaluated with CIPAC method MT185 (wet sieve test). A sample of the formulation is dispersed in water and the resulting suspension is transferred to a sieve of, for example, 200 mesh size and washed. The amount of material retained on the sieve is determined by drying and weighing.

[0153] Furthermore, the copolymer according to the invention makes it possible to reduce the pressure of the agricultural composition during possible granulation, compared to the pressure during granulation of the same agricultural composition to which no copolymer according to the invention is added.

[0154] Granulation is a process for preparing water dispersible granule formulations. In the granulation process, after grinding one or more agricultural materials with solid additives, a certain amount of water (up to 30% w / w) is added. The copolymer according to the invention is added together with this water. The powder is then introduced into a granulator. The granulator, consisting of wings rotating at a certain speed (determined by the user), pushes the powder through a screen with small holes. In extreme cases, the powder can generate a great pressure to prevent this transfer through the screen.

[0155] The copolymer layer formed on the granules using the copolymer according to the invention can improve granulation by significantly reducing the pressure generated during the granulation process.

[0156] In another aspect of the present invention there is provided the use of the biodegradable polyester as defined above as a dispersant for an agricultural composition.

[0157] Furthermore, the present invention relates to the use of an agrochemical composition as described previously for treating soil, plants and / or seeds for controlling harmful organisms and / or regulating plant growth.

[0158] The present invention also relates to a method for treating soil, plants and / or seeds to control pests and / or regulate plant growth by applying a composition according to the invention as previously described to at least one plant, an area adjacent to plants, soil suitable for supporting plant growth, plant roots, plant foliage, and / or seeds suitable for producing plants.

[0159] Application of the compositions according to the invention makes it possible to kill or inhibit pests and / or to clean and / or inhibit the growth of undesirable vegetation.

[0160] The agrochemical composition according to the present invention can be diluted and applied in a conventional manner to at least one plant, an area adjacent to a plant, soil suitable for supporting plant growth, the roots of a plant, the leaves of a plant, and / or seeds suitable for producing a plant; for example, by watering (drenching), drip irrigation, spraying, and / or atomization.

[0161] Should the disclosure of any patents, patent applications, and publications incorporated herein by reference conflict with the description of the present application to the extent that it might render a term unclear, the present invention shall take precedence.

[0162] Examples

[0163] Biodegradable polyester

[0164] Biodegradable polyesters are prepared by the following process:

[0165] A stainless steel reactor equipped with an overhead stirrer, nitrogen inlet, condenser assembly with receiving vessel and solid addition port was charged with 384.2 g (2.209 mol) of 1,4-cyclohexanedicarboxylic acid, 155.9 g (0.552 mol) of 5-sulfoisophthalic acid sodium salt, 3.49 g (0.011 mmol) of (triethanolamine) isopropoxide titanium (IV) solution (80 wt.% in isopropanol) [Tyzor TE] and 519.4 g (8.28 mol) of ethylene glycol. The mixture was heated to 160° C. under a nitrogen blanket and the reaction mixture was maintained at the same temperature for 60 minutes with stirring, then the reaction temperature was increased to 200° C. and a reduced pressure of 100 mbar was gradually reached, under which conditions ethylene glycol began to distill and was collected in a receiver. The reaction temperature was then increased to 235° C. under reduced pressure. When the reaction reached 235°C, the pressure was further reduced to 20 mbar. The reaction was maintained under this condition for 60 minutes, after which the temperature was reduced to stop the polymerization. The polymer was discharged after it reached room temperature.

[0166] Table 1: Biodegradable polyesters prepared

[0167]

[0168] CHDA – Cyclohexanedicarboxylic acid

[0169] SSIA – 5-sulfoisophthalic acid sodium salt

[0170] TA – Phthalic acid

[0171] EG – Ethylene glycol

[0172] 2. Biodegradability test

[0173] The biodegradability test was carried out according to the inherent biodegradability test using OECD 302B.

[0174] If the biodegradability test result is over 70% based on the theoretical oxygen demand, or ThOD, calculation, and meets the validity criteria of the test, it is considered to have passed the readily biodegradable test.

[0175] Table 2: Biodegradability test results

[0176]

[0177] According to Table 2, all polyesters are biodegradable.

[0178] Agricultural compositions

[0179] Imidacloprid 48% SC of the present invention is prepared as follows:

[0180] -Put DM water into a container, add propylene glycol, Proxel GXL, Gensil 2030 (partial amount).

[0181] - Now add the dispersant and Rhodasurf LA 9, mix well until the solution is homogeneous and the surfactant is properly dissolved.

[0182] -Slowly add imidacloprid and mix until uniform.

[0183] - Now start grinding the slurry obtained above in a bead mill and keep cooling water circulation between 20°C and 30°C during grinding.

[0184] - Check the particle size at an intermediate stage. If suitable, transfer it to another container.

[0185] - Add Gensil 2030 (if needed) under slow stirring to remove trapped foam. Check that density is within specification.

[0186] - Add required amount of 2% Agrhopol 23W solution to the milled slurry.

[0187] After the compositions were obtained, they were then subjected to dispersion tests. As shown in Table 3, all the polyesters of the present invention showed favorable dispersant properties and were even superior to Geropon DA 1349 currently sold on the market.

[0188]

[0189] Carbendazim 46.27% SC of the present invention was prepared as follows:

[0190] -Put DM water into a container, add propylene glycol, Proxel GXL, Gensil 2030 (partial amount).

[0191] - Now add the dispersant and Rhodasurf LA 9, mix well until the solution is homogeneous and the surfactant is properly dissolved.

[0192] -Slowly add carbendazim and mix until smooth.

[0193] - Now start grinding the slurry obtained above in a bead mill and keep cooling water circulation between 20°C and 30°C during grinding.

[0194] - Check the particle size at an intermediate stage. If suitable, transfer it to another container.

[0195] - Add Gensil 2030 (if needed) under slow stirring to remove trapped foam. Check that density is within specification.

[0196] - Add required amount of 2% Agrhopol 23W solution to the milled slurry.

[0197] The dispersion test results are shown below in Table 4. As shown, Geropon is not biodegradable and the dispersion performance of S1 is comparable to that of Geropon.

[0198] Diuron 80% WDG of the present invention was prepared as follows:

[0199] - jet milling to obtain a fine powder of the ingredient diuron;

[0200] - Weigh the ingredients diuron, dispersant (S4), wetting agent (GEROPON L-WET F) and filler (sodium benzoate, starch, EDTA-2Na) according to the proportion and put them into a plastic mixer. Mix at high speed until homogeneous;

[0201] -Add appropriate amount of water and mix at high speed until smooth;

[0202] - putting wet powder into an extruder and obtaining wet granules;

[0203] - Dry in a 60°C oven for 2 hours to ensure moisture is below 1%.

[0204] Imidacloprid 70% WDG of the present invention is prepared as follows:

[0205] - jet milling to obtain a fine powder of the ingredient imidacloprid;

[0206] - Weigh the ingredients imidacloprid, dispersant (S4), wetting agent (GEROPON L-WET F) and fillers (sodium gluconate, EDTA-2Na) and place them in a plastic mixer; mix at high speed until homogeneous;

[0207] -Add appropriate amount of water and mix at high speed until smooth;

[0208] - placing the wet powder into an extruder and obtaining wet granules;

[0209] - Dry in a 60°C oven for 2 hours to ensure moisture is below 1%.

[0210] Atrazine 87% WDG of the present invention was prepared as follows:

[0211] - jet milling to obtain a fine powder of the ingredient atrazine;

[0212] - Weigh the ingredients atrazine, dispersant (S4), wetting agent (GEROPON L-WET F) and filler (EDTA-2Na) and place them in a plastic mixer; mix at high speed until homogeneous;

[0213] -Add appropriate amount of water and mix at high speed until smooth;

[0214] - putting wet powder into an extruder and obtaining wet granules;

[0215] - Dry in a 60°C oven for 2 hours to ensure moisture is below 1%.

[0216] Table 5 shows that the dispersants of the present invention can also be used in WDG formulations and impart favorable suspension properties to WDG formulations containing them.

[0217]

Claims

1. A biodegradable polyester for use as a dispersant for agricultural formulations, prepared from a monomer composition comprising: (a) a sulfonated dicarboxylic acid monomer (SA) selected from the group consisting of: at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof; (b) a polyhydroxy polyol (P) selected from the group consisting of at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethylene oxide value in the range of 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units; and (c) a dihydroxy compound (DH) selected from C5-C 10 Alicyclic diols, C5-C 10 Cycloaliphatic diacids, C2-C8 hydroxylated aliphatic acids, or combinations thereof.

2. The biodegradable polyester for use as a dispersant according to claim 1, wherein The monomer composition further comprises: (d) a diacid component, which is at least one selected from the group consisting of: d1) an unsulfonated dicarboxylic acid monomer (A) consisting of at least one dicarboxylic acid or a derivative thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and furandicarboxylic acid; and d2) Polyester prepolymers prepared from the unsulfonated dicarboxylic acid monomers (A) or derivatives thereof and the polyhydric polyols (P).

3. The biodegradable polyester for use as a dispersant according to claim 1 or 2, wherein The sulfonated dicarboxylic acid monomer (SA) is one or more selected from the group consisting of sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydride, 4-sulfo-2,7-naphthalene dicarboxylic acid or anhydride, sulfo-4,4'-bis(hydroxycarbonyl)diphenyl sulfone, sulfodiphenyl dicarboxylic acid or anhydride, sulfo-4,4'-bis(hydroxycarbonyl)diphenylmethane, sulfo-5-phenoxyisophthalic acid or anhydride, sulfosuccinic acid or anhydride or its lower diesters.

4. The biodegradable polyester for use as a dispersant according to claim 1 or 2, wherein The polyhydric alcohol (P) is selected from ethylene glycol or glycerol.

5. The biodegradable polyester for use as a dispersant according to claim 1 or 2, wherein The dihydroxy compound (DH) is present in an amount ranging from 0.1% to 50%, preferably from 0.5% to 25%, more preferably from 0.5% to 15%, based on 100 mol% of the biodegradable polyester used as a dispersant.

6. The biodegradable polyester for use as a dispersant according to any one of claims 1 to 5, wherein The dihydroxy compound (DH) is selected from cyclohexanedimethanol and cyclohexanedicarboxylic acid.

7. A biodegradable polyester for use as a dispersant for agricultural formulations, wherein the biodegradable polyester comprises the following repeating units (I) and (II): wherein R1, R2, R3, and R4 are independently selected from H or C1-C8 alkyl; A is selected from C5-C 10 an alicyclic group or an aromatic group; and n and m are numbers in the range of 1 to 200.

8. The biodegradable polyester for use as a dispersant for agricultural formulations according to claim 7, wherein One of R1 and R2 is selected from H, and the other is selected from H, methyl, ethyl, propyl, or butyl.

9. The biodegradable polyester for use as a dispersant for agricultural formulations according to claim 7 or 8, wherein The biodegradable polyester further comprises repeating units (III) wherein R5 and R6 are independently selected from H or C1-C8 alkyl; and p is a number in the range of 1 to 200.

10. The biodegradable polyester for use as a dispersant for agricultural formulations according to claims 7 to 9, wherein The biodegradable polyester further comprises at least one of repeating units IV to VI, wherein A is as defined above, and B is selected from C5-C 10 Alicyclic group.

11. The biodegradable polyester for use as a dispersant for agricultural formulations according to claim 10, wherein B is selected from hexamethylene.

12. The biodegradable polyester for use as a dispersant for agricultural formulations according to claims 7 to 11, wherein A is selected from hexamethylene.

13. An agricultural composition comprising: (I) agricultural materials; and (II) The biodegradable polyester according to any one of claims 1 to 12.

14. The agricultural composition according to claim 13, wherein The agricultural composition is formulated as an emulsifiable concentrate (EC), an emulsion in water concentrate (EW), a suspension concentrate (SC), a capsule suspension (CS), a ZC formulation, a flowable concentrate for seed treatment (FS), a water dispersible granule (WDG) or a suspoemulsion (SE).

15. The agricultural composition according to claim 13, wherein The biodegradable polyester is present in an amount ranging from 0.1 wt.% to 5 wt.%, preferably from 0.2 wt.% to 3 wt.%, more preferably from 0.5 wt.% to 1 wt.%, based on the total weight of the agricultural composition.

16. The agricultural composition according to claim 13, wherein The biodegradable polyester is present in an amount ranging from 3 wt % to 20 wt %, preferably from 4 wt % to 10 wt %, based on the total weight of the agricultural composition.

17. Use of the biodegradable polyester according to any one of claims 1 to 12 as a dispersant for agricultural formulations.

18. Use of the agricultural composition according to any one of claims 13 to 15 for treating soil, plants and / or seeds to control harmful organisms and / or regulate plant growth.

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