BR112021007479A2 - oily dispersion of dithiocarbamate, and method for the treatment of plants, crops and/or fields - Google Patents

Abstract

OILY DISPERSION OF DITHIOCARBAMATE, AND, METHOD FOR THE TREATMENT OF PLANTS, CROP AND OR FIELDS. Oily dispersion of dithiocarbamate comprising a polyamide obtained by reacting a fatty acid, a polyamine and a di-or tricarboxylic acid in a specific molar ratio and using the same in agriculture.

Description

1 / 28 OILY DISPERSION OF DITHIOCARBAMATE, E, METHOD FOR THE TREATMENT OF PLANTS, CROP AND OR FIELDS

TECHNICAL FIELD

[001] The present invention relates to an oily dispersion of dithiocarbamate comprising a polyamide obtained by reacting a fatty acid and a di or tricarboxylic acid with a polyamine in a specific molar ratio.

[002] This invention also concerns the use in agriculture of the oily dispersion of dithiocarbamate comprising the polyamide mentioned above.

PRIOR TECHNIQUE

[003] Dithiocarbamates (DTC) are mostly from the important group of organic fungicides to control plant diseases. DTCs are distinguished by a broad spectrum of activity against various plant pathogens, low acute mammalian toxicity, and low production costs. Due to their known chemical instability at elevated temperature in the presence of moisture, dithiocarbamate active substances are, as a rule, formulated as solid formulations such as dispersive powders and granules or as oily dispersions.

[004] Agrochemical oil dispersions (OD) are stable suspensions of agrochemical active ingredients, such as pesticides and crop protection chemicals, in organic fluids and are usually intended for dilution with water before use. Oily dispersions are particularly useful for formulating solid insoluble oily active ingredients and for formulating unstable compounds in aqueous compositions, such as dithiocarbamates.

[005] A disadvantage of OD formulations, in particular of dithiocarbamates, is that such formulations are not stable long enough and show phase separation on storage. Thus, the storage

2 / 28 even at ambient temperatures often leads to the effects of aggregation, viscosity formation, gel formation or pronounced sedimentation of the suspended phase. In the worst cases, the effects are irreversible, that is, even strong shear, for example by agitation, cannot re-homogenize the formulation.

[006] A common method to solve this problem is usually to add to the dispersions a stabilizer that can act as a thickener increasing the viscosity of the system and/or can act as a dispersant reducing the sedimentation rate of the particles.

[007] Typical stabilizers for dry organic systems include organic clays such as Bentone®. Organic clays are manufactured from natural smectite, hectorite or montmorillonite clays by reacting the hydrophilic clay with quaternary ammonium compounds so that it becomes organophilic and therefore compatible with non-aqueous media.

[008] Known stabilizers are surfactants, vegetable oil derivatives, silica derivatives and synthetic polymers.

[009] For example, WO 2000/072681 describes an essentially anhydrous dithiocarbamate liquid formulation comprising: at least one active ingredient from the class of dithiocarbamates, an essentially anhydrous oil phase, a polyhydroxystearic acid or a derivative thereof and/ or an alkyl or alkenyl glycerin ether ethoxylate, as stabilizers, and optionally an anionic surfactant.

[0010] US 2009/202648 describes a dispersion comprising: a dispersed phase comprising ethylene bis(dithiocarbamate); a continuous phase comprising a water-immiscible liquid; and, as a stabilizer, a metallic polyacrylate having a molecular weight of from about 150 to about 15,000 Daltons.

[0011] The document US 2011/237591 refers to fungicidal plant protection formulations comprising: a) dimethomorph and b) hair

3 / 28 minus a dithiocarbamate, formulated as a suspension of concentrated oil in a liquid organic diluent and in the presence of at least one surface-active substance. Silicates, modified silicates, organic thickeners, for example those based on hydrogenated fatty acids and fatty acid derivatives, and thickeners based on synthetic polymers are mentioned among the suitable stabilizers.

[0012] WO 2012/167322 refers to an oil-based agricultural suspension formulation comprising an active ingredient suspended in finely divided form in an oil; and, as stabilizer, at least one surfactant selected from a fatty acid polyalkylene glycol ether condensate or a fatty acid polyalkylene glycol ether condensate. Dithiocarbamates are mentioned among the active ingredients.

[0013] WO 2016/153913 describes an agrochemical formulation comprising a pesticide or mixture of pesticides, among which dithiocarbamates and an adjuvant composition comprising an oil and a maleated natural oil derivative obtained from the reaction of a maleated natural oil and a composite derivative comprising at least one polyoxyalkylene glycol, monoalkyl polyoxyalkylene glycol, polyether amine, alkylene amine, alkanol amine, etc. Polyamines, such as ethylene diamine, diethylene tetramine, triethylene diamine and triethylene tetramine, are included among the alkylene amines.

[0014] Unfortunately, all these stabilizers show disadvantages and problems that reduce their applicability and performance

[0015] They do not always communicate sufficient stability for dispersions across the desired temperature range and for sufficient time.

[0016] Since they can significantly increase the viscosity of the dispersion, they must be very carefully dosed.

[0017] Organic clays have to be carefully dispersed and

4 / 28 require the presence of a chemical activator in order to function as anti-sedimentation agents. If the organic clay is not well dispersed or chemically activated the result is poor cohesive strength and consequently limited physical stability of the product.

[0018] Furthermore, handling of most of these stabilizers is very difficult and/or harmful because they are mostly very fine, light powders or extremely viscous liquids.

[0019] Finally, they are difficult to dissolve/homogenize in dispersions while avoiding the formation of gels or lumps and continuous and careful monitoring of the formulation process is required.

[0020] For these reasons, a need still exists for a stabilizer that improves the physical stability of oily dispersions of fungicides of the dithiocarbamates family without presenting the problems mentioned above.

[0021] We have found that oily dispersions of dithiocarbamates can be stabilized using a water-soluble polyamide obtained by reacting in a specific ratio of a fatty acid and a polyamine and subsequently reacting the obtained aminoamide with a di- or tricarboxylic acid.

[0022] This polyamide facilitates the preparation of oily dispersions of dithiocarbamate and its storage, even in hot climates, for its effective use in agronomic applications.

[0023] Polyamides have already been proposed as a stabilizer for agrochemical oil dispersions.

[0024] The document WO 2012/080208 describes a method for the preparation of an oily dispersion of an agrochemical product comprising a thickener which is an amide obtained by the reaction of a polyhydroxystearic acid with diethylene triamine and/or triethylene tetramine. Dithiocarbamates are mentioned among the various agrochemical compounds

5 / 28 suitable for the preparation of oily dispersions.

[0025] WO 2015/145105 describes an oily dispersion comprising an oil, at least one agrochemical active and/or nutrient and a polyamide formed from a dimeric acid compound, optionally a C4-C12 codicarboxylic acid and one or more diamine compounds. The agrochemical active can be chosen from a very long list of pesticides, including fungicides, herbicides, insecticides, algaecides, molluscicides, miticides and rodenticides; and antimicrobials, including germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoa and antiparasites.

[0026] As far as the Applicant is aware, none of the prior art documents describe the use of the specific polyamides of the invention as stabilizers for oily dispersions of dithiocarbamate.

[0027] The expression "oily dispersion of dithiocarbamate" is to be understood as meaning a concentrated dispersion based on an organic vehicle in which one or more compounds of dithiocarbamate are suspended; additional agrochemical active ingredients may be present in the dispersion.

DESCRIPTION OF THE INVENTION

[0028] It is therefore an object of the present invention an oily dispersion of dithiocarbamate comprising: from 5.0 to 60% by weight (% by weight) of at least one fungicide of the dithiocarbamates family, from 10 to 90% by weight of an oil and from 0.05 to 10% by weight of a polyamide obtained by the reaction in a first step: a) one mole of a polyamine having n amino groups with exchangeable hydrogens, where n is an integer ranging from 3 to 4; b) from 1 to n-1 mol of a saturated or unsaturated aliphatic C6-C30 monocarboxylic acid or an ester thereof; to get an aminoamide having an acid number below

6/28 of 30 mgKOH/g and subsequently reacting the remaining amino groups carrying exchangeable aminoamide hydrogens with: c) from 0.3 to 1.0 mol of a C2-C10 di- or tricarboxylic acid or with the corresponding anhydride for each mol of remaining amino groups to obtain a polyamide with a total amine value below 60 mgKOH/g.

[0029] It is a further object of the invention a method for the preparation of an oily dispersion of dithiocarbamate comprising: i) preparing a mixture comprising at least one fungicide of the dithiocarbamates family and an oil; ii) adding the polyamide described above to the mixture; said oily dispersion of dithiocarbamate comprising from 5.0 to 60% by weight of said fungicide, from 10 to 90% by weight of oil and from 0.05 to 10% by weight of said polyamide.

[0030] It is another object of the invention a method for the treatment of plants, crops or fields comprising the step of: i. providing an oily dispersion of dithiocarbamate as described above; ii. diluting said oily dispersion of dithiocarbamate with water or an aqueous solution of agronomic compounds to produce a sprayable composition; iii. applying to plants, crops or fields an effective amount of said sprayable aqueous composition.

DETAILED DESCRIPTION OF THE INVENTION

[0031] Preferably, the oil dispersion of dithiocarbamate of the invention comprises: from 7 to 60% by weight of at least one fungicide of the family of dithiocarbamates; from 20 to 80% by weight of an oil and from 0.1 to 5.0% by weight, more preferably from 0.2 to 3% by weight, of the polyamide described above.

7/28

[0032] The fungicide of the dithiocarbamates family can be chosen, for example, from amobam, assomate, azitiram, carbamorf, cufraneb, cuprobam, disulfiram, ferbam, metam, nabam, tecoram, tiram, urbacida, ziram, dazomet, etem, milneb , mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb. The preferred fungicides of the dithiocarbamates family are: mancozeb, maneb, tira and ziram. Mancozeb being the most preferred.

[0033] Oil is a water-insoluble liquid organic medium and can be any of those oils commonly used in agriculture to make oily dispersions for use in agriculture. Suitable oils for the dispersions of the invention are, for example: • linear or branched C8 to C30 paraffins having boiling points above 140°C (paraffin oils), for example octane, nonane, decane, undecane, dodecane, tridecane, tetradecane , pentadecane, hexadecane, their mixtures or mixtures thereof with higher boiling homologues such as hepta-, octa-, nonadecane, eicosan, henoicosan, docossan, tricossan, tetracossan, pentacosane and the branched chain isomers thereof.

[0034] • mineral oils, which are distilled fractions of mineral oil (petroleum), such as C14 to C30 hydrocarbon mixtures of straight or branched open chain.

[0035] • C7 to C18 aromatic or cycloaliphatic hydrocarbons, which may be unsubstituted or substituted, such as substituted mono- or polyalkyl benzenes or substituted mono- or polyalkyl naphthalenes.

[0036] • vegetable oils such as liquid triglycerides eg olive oil, castor oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, cottonseed oil soy, rapeseed oil, linseed oil, sunflower oil, safflower oil or also products from the transesterification of

8/28 the same, for example, alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester.

[0037] • animal oil, such as whale oil, cod liver oil or mink oil.

[0038] • liquid esters of C1 to C12 monoalcohols or polyols, for example butanol, n-octanol, i-octanol, dodecanol, cyclopentanol, cyclohexanol, cyclooctanol, ethylene glycol, propylene glycol or benzyl alcohol, with carboxylic or polycarboxylic acids C2 to C10, such as caproic acid, capric acid, caprylic acid, pelargonic acid, succinic acid and glutaric acid; or with aromatic carboxylic acids such as benzoic acid, toluic acid, salicylic acid and phthalic acid. Esters which can be used in the oil dispersions of the invention are thus, for example, benzyl acetate, caproic acid ethyl ester, pelargonic acid ethyl ester, benzoic acid methyl or ethyl ester, salicylic acid methyl, propyl or butyl ester phthalic acid diesters with C1 to C12 saturated aliphatic or alicyclic alcohols such as phthalic acid dimethyl ester, dibutyl ester, di-iso-octyl ester; • liquid amides of amines, such as C1-C5 alkylamines or alkanolamines, with C6-C18 carboxylic acids; • mixtures thereof.

[0039] According to a particular modality, the oil is chosen among paraffin oils, mineral oils, in particular those having an aromatic portion of less than 8% by weight, vegetable oils or transesterification products thereof and mixtures thereof .

Polyamine a) has n amino groups with interchangeable hydrogens, where n is an integer ranging from 3 to 4. More preferably n is 3.

Preferred polyamines include polyalkylene polyamines, for example those having the formula I:

9 / 28 H2N[(CH2)xNH]yH I where x is an integer ranging from 1 to 6 and y is an integer ranging from 2 to 3.

[0042] Examples of preferred polyalkylene polyamines of formula I are those wherein x is 2, i.e. the polyethylene amines such as ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine and mixtures thereof.

[0043] Other preferred polyalkylene polyamines are polyethylene imines with an average molecular weight below about 300 daltons, which exhibit a low degree of branching.

[0044] More preferably, polyamine a) is a polyethylene amine chosen from diethylene triamine, triethylene tetramine and mixtures thereof. Diethylene triamine being most preferred.

The aliphatic C6-C30 monocarboxylic acid b) (or its ester) can be both unsaturated and saturated.

Examples of C6–C30 unsaturated aliphatic monocarboxylic acids suitable for preparing the polyamide of the invention include both unsaturated and polyunsaturated aliphatic carboxylic acids having 6 to 30 carbon atoms. Examples of these acids are palmitoleic acid, oleic acid, linoleic acid, licolenic acid, arachidonic acid and the like.

[0047] Examples of saturated aliphatic C6–C30 monocarboxylic acids include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and the like.

[0048] Mixtures of C6-C30 saturated and unsaturated aliphatic monocarboxylic acids can also be used.

[0049] In a preferred embodiment of the invention, the C6–C30 monocarboxylic acid b) is a mixture of C12-C22 saturated and unsaturated aliphatic monocarboxylic acids.

10 / 28

[0050] In a more preferred embodiment of the invention the C6-C30 monocarboxylic acid b) is a mixture of C12-C22 saturated and unsaturated aliphatic monocarboxylic acids comprising at least 40% by weight, preferably at least 60% by weight, of oleic acid .

[0051] Natural oils, such as coconut oil, mustard seed oil, palm oil, olein, soybean oil, canola oil, tall oil, sunflower oil and mixtures thereof, are particularly preferred sources of the monocarboxylic acid or mixtures thereof.

[0052] The mixtures of monocarboxylic acids obtained as a by-product in the biodiesel production process are also suitable sources of aliphatic saturated and unsaturated C6-C30 monocarboxylic acids.

[0053] In a preferred embodiment of the invention the polyamine is reacted with a saturated or unsaturated aliphatic C6–C30 monocarboxylic acid or a mixture of aliphatic C6–C30 monocarboxylic acids.

[0054] Preferably, the monocarboxylic acid source is selected from tall oil, rapeseed oil, soybean oil, by-products in the biodiesel production process and mixtures thereof.

[0055] The preparation of the aminoamide can be carried out according to methods well known to those skilled in the art. For example, heating the polyamine a) and the monocarboxylic acid b) (or an ester thereof) to 250°C, preferably from 140 to 180°C, each in a suitable hydrocarbon solvent such as toluene or xylene or not and subjected to azeotropy of the formed water, with or without catalysts such as p-toluenesulfonic acid, zinc acetate, zirconium naphthenate or tetrabutyl titanate. Usually, the end point of the reaction is considered to be reached when the acid number of the reaction mixture, determined by the ASTM standard method D1980-87, is below 30 mgKOH/g, preferably below 10 mgKOH/g.

11/28

[0056] When the polyamine used is diethylene triamine, preferably in the first step one mole of diethylene triamine is reacted with 1.4 to 2.0 moles of aliphatic C6-C30 monocarboxylic acid.

The di- or tricarboxylic acid or the corresponding anhydride c), which can be reacted with the aminoamides described above to form the polyamide of the present invention, preferably has from 3 to 8 carbon atoms, more preferably 4 carbon atoms.

[0058] Examples of suitable C2-C10 di- or tricarboxylic acids include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid, carboxymethyloxysuccinic acid and lactoxysuccinic acid; phthalic acid; and mixtures thereof.

[0059] Preferably, the C2-C10 di or tricarboxylic acid c) is a C3-C8 dicarboxylic acid. Dicarboxylic acids which are particularly suitable for carrying out the present invention are fumaric acid, malonic acid, maleic acid or their corresponding anhydrides; and mixtures thereof. Maleic acid being most preferred.

[0060] The aminoamide containing amino groups with exchangeable hydrogens and the di- and/or tricarboxylic acid (or corresponding anhydride) described above can be condensed at a temperature ranging from about 120 to about 250°C, preferably about about 250°C. 140 to about 200°C, while the water formed is distilled off. The reaction endpoint is considered to be reached when the total amine value of the reaction mixture, determined by the ASTM standard method D2074-12, is below 60 mgKOH/g, preferably below 40 mgKOH/g, more preferably below 20 mgKOH/ g.

[0061] Preferably, the acid number of the polyamide thus obtained, determined by the ASTM standard method D1980-87, is below 70 mgKOH/g, more preferably it is comprised between 20 and 60

12 / 28 mgKOH/g.

[0062] In a preferred embodiment of the invention, the remaining amino groups with exchangeable hydrogens are reacted with 0.4 to 0.9 mol, more preferably 0.4 to 0.7 mol, of C2-C10 di- or tricarboxylic acid, preferably dicarboxylic acid, for every mole of amino groups remaining.

[0063] The polyamide obtained by the reaction of: a) one mole of diethylene triamine; b) from 1.4 to 2 mol of a mixture of C12 -C22 saturated or unsaturated aliphatic monocarboxylic acids or esters thereof; and, subsequently, reacting the remaining amino groups with exchangeable hydrogens of the aminoamide thus obtained with: c) from 0.4 to 0.7 mol of maleic acid or with the corresponding anhydride for each mol of remaining amino groups; it is particularly suitable for carrying out the present invention.

[0064] The polyamide described above shows unexpectedly high stabilizing performances for oily dispersions of dithiocarbamate, especially with vegetable oils and paraffin oils.

[0065] In a preferred embodiment, the oil dispersion of dithiocarbamate of the invention further comprises from 5 to 30% by weight, preferably from 5 to 20% by weight, of at least one surfactant. Surfactants are used not only to improve dispersion, emulsify oil on dilution in water, but also to increase suspension stability, wettability and penetration and to provide the mixability and suspension/emulsion stability of a product after dilution. with water.

[0066] As surfactants, anionic, cationic, non-ionic and ampholytic surfactants and mixtures thereof can be used. the surfactants

Suitable are, for example, non-ionic emulsifiers and dispersants, such as: • polyalkoxylated aliphatic alcohols, for example polyethoxylated and/or polypropoxylated, saturated and unsaturated, such as those having 8 to 24 carbon atoms in the alkyl radical and having 1 to 50, preferably 3 to 20, ethylene oxide and/or propylene oxide units; • polyalkoxylated arylalkylphenols, such as, for example, polyalkoxylated triestyrylphenol having an average degree of alkoxylation between 3 and 50, preferably from 5 to 25; • polyalkoxylated alkylphenols, such as those having one or more alkyl radicals, such as, for example, polyalkoxylated nonylphenol or tri-sec-butylphenol and a degree of alkoxylation of between 2 and 40, preferably of 4 to 20; • hydroxyl fatty acids or polyalkoxylated glycerides which contain hydroxyl fatty acids, such as, for example, castor oil, having a degree of alkoxylation of between 10 and 80; • sorbitan or sorbitol esters with fatty acids or polyalkoxylated sorbitan or sorbitol esters; • polyalkoxylated amines; • di- and triblock copolymers, for example of alkylene oxides, for example of ethylene oxide and propylene oxide, having an average molar mass from 200 to 8000 g/mol, preferably from 1000 to 4000 g/mol; • alkylpolyglycosides or polyalkoxylated alkylpolyglycosides.

[0067] Preferred nonionic surfactants are saturated and unsaturated, aliphatic, polyalkoxylated alcohols, in particular alkoxylated aliphatic alcohols having 8 to 14 carbon atoms in the alkyl radical and 3 to 20 ethylene oxide and/or propylene oxide units, arylalkylphenols

14 / 28 polyalkoxylates and di- and triblock copolymers, in particular polyethylene oxide/polypropylene oxide block copolymers having an average molar mass of 1000 to 4000 g/mol.

[0068] Also suitable are anionic surfactants, for example: • polyalkoxylated surfactants which are ionically modified, for example by converting the terminal free hydroxyl function of the alkylene oxide block into a sulfate or phosphate ester; • alkali metal and alkaline earth metal salts of alkylarylsulfonic acids having a straight-chain branched alkyl chain; • alkali metal and alkaline earth metal salts of paraffin sulfonic acids and chlorinated paraffin sulfonic acids; • polyelectrolytes, such as lignosulfonates, naphthalenesulfonate and formaldehyde condensates, and polystyrenesulfonates; • anionic alkylpolyglycoside esters, such as sulfosuccinates or alkylpolyglycoside citrates; • sulfosuccinic acid salts, which have been esterified once or twice with linear or branched aliphatic, cycloaliphatic and/or aromatic alcohols or sulfosuccinic acid salts, which have been esterified once or twice with alkylene oxide adducts of alcohols.

[0069] Preferred anionic surfactants are nonionic polyalkoxylated surfactants which have been ionically modified, salts of alkylarylsulfonic acids having a straight branched chain alkyl chain and anionic esters of alkylpolyglycosides.

[0070] Examples of cationic and ampholytic surfactants are quaternary ammonium salts, alkyl amino acids and betaine or imidazoline amphotensides.

[0071] Nonionic surfactants are the preferred surfactants for carrying out the present invention.

[0072] The oily dispersion of dithiocarbamate of the invention can

15/28 further comprise from 0.55 to 50% by weight, preferably from 2 to 30% by weight, of at least one other agrochemical active ingredient.

[0073] Additional agrochemical active ingredients suitable for the oily dispersion of dithiocarbamate are, for example, fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, arachnicides, insect growth regulators, repellents, antibiotics, plant growth regulators, additional plant nutrients and mixtures thereof.

[0074] Examples of fungicides which may be mentioned are: 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2',6'-dibromo-2-methyl-4'-trifluoro-methoxy-4'-trifluoromethyl-1,3-thiazol-5-carboxanilide; 2,6-dichloro-N-(4-trifluoro-methylbenzyl)-benzamide; (E)-2-methoximino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulfate; (E) methyl-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]-methyl acetate; 2-phenylphenol (OPP), aldimorph, ampropylphos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacril, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, butiobate, calcium polysulfide,captafol,captane,carboxyquinendazim , chlorneb, chloropicrin, chlorothalonil, clozolinate, cymoxanil, cyproconazole, ciprofuram, carpropamide, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dichloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diphenylon doniconazole , edifenphos, epoxiconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fentin acetate, fentin hydroxide e, ferinzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, follanethyl, sulfolamide, fluto aluminum, phthalide, fuberidazole, furalaxyl, phenexamide, guazatine, hexachlorobenzene, hexaconazole, hyexazole, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodion, isoprothiolan, iprovalicarb, cassugamycin, copper preparations such as: copper hydroxide,

16 / 28 copper naphthenate, copper oxychloride, copper sulfate, copper oxide, copper oxine and Bordeaux mixture; mepanipyrim, mepronil, metalaxyl, metconazol, metasulfocarb, metfuroxam, metsulfovax, midobutanil, nitrothalisopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazol, pencicuron, fosdiclon, proben, pimaricin propiconazole, pyrazolophos, pyrifenox, pyrimethanil, pyroquilon, quintazene (PCNB), quinoxyphene, sulfur and sulfur preparations, tebuconazole, teclophthalam, technazene, tetraconazole, thiabendazole, thiciofen, thiophanate-methyl, toldlophos-methyl, trimenadioxide, trimenadime , triclamide, tricyclazole, tridemorph, trifiumizole, triforin, triticonazole, triphyoxystrobin, validamycin A, vinclozolin, cyproconazole, dodine, fenamidone, fenoxamide, fluopicolide, fluoxastrobin, fosetyl-aluminium, iprovalicarb, spidium, triconoxystrobin, triconoxystrobin acibenzolar-S-methyl, cyprodinil, mandipropamid, fenpropidin, boscalid, kresoxim-methyl, pyraclostrobin, dimethomorph, fenpropimorph, metraphenone, tolclophos-methyl and 2-[2-(1-chloro-cyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2 ,4]-triazol-3-thione.

Examples of bactericides which may be mentioned are: bronopol, dichlorofenp, nitrapirin, cassugamycin, octilinon, furancarboxylic acid, oxytetracycline, probenazol, streptomycin, teclophthalam, copper sulfate and other copper preparations.

[0076] Examples of insecticides, acaricides and nematicides that may be mentioned are: abamectin, acephate, acrinathrin, alanicarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4 -bromo-2-(4-chlorphenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile, bendiocarb, benfuracarb,bensultap, betacifluthrin, bifenthrin, BPMC, brofenprox, bromofosa, bufencarb,

17 / 28 buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, cloetocarb, clarethoxyphos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl] cyano-N-methyl-ethanoimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocithrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S-demeton-S, , diafenthiuron, diazinon, diclofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxation, disulfoton, emamectin, esfen valerate, etiofencarb, ethion, etofenprox, ethoprophos, phenazine oxide, etrinphos fenobucarb, fenothiocarb, fenoxycarb, fenpropatrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazuron, flucicloxuron, flucitrinate, flufenoxuron, flufenprox, fluvalinate, phonofos, formotion, furthiocarb, H, fubfen heptenophos, bexaflumuron, hexythiazox, imidacloprid, iprobenphos, isazophos, isofenphos, isoprocarb, isoxation, ivermectin, lambdacibalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, milbectomyl, methamethyphos, metcarbethion, methacriphos moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxidemeton M, oxideprophos, parathion AL, parathion ML, permethrin, fentoate, phorate, phosalon, fosmet, phosphamidon, phoxim, pirimicarb, pyrimiphos M, pirimiphos, A, profane propapbos, propoxur, prothiophos, protoate, pymetrozine, pyraclophos, pyridafenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, salithion, ebufos, silafluofen, sulfotep, sulprofos, tebufenthion, tebufenidium, tebufenozide terbufos, tetrachlorvinphos, thiacloprid, thiafenox, thiamethoxam, thiodicarb, thiophanox, thiometon, thionazine, thuringiensin, tralomethrin, transfluthrin, triaraten, triaz ofos, triawron, trichlorfon, triflumuron, trimetacarb, vamidothion, XMC, xylylcarb, zetamethrin, etoprophos, fenpyroximate, methoxyfenozide, spinosad,

18 / 28 spirodiclofen, thiacloprid, cypermethrin, alpha cypermethrin, alphamethrin and metaflumizone.

[0077] Examples of herbicides which may be mentioned are: anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichlorpicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as, for example, 2,4-D, 2,4-DB, 2,4-DP, Fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic acid esters such as, for example, diclofop-methyl, fenoxapropethyl, Fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phennedipham and profam; chloroacetanilides, such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroarylines, such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafene, lactofen and oxyfluorfen; ureas, such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and metabenzthiazuron; hydroxylamines such as, for example, aloxydim, clethodim, cyclooxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazametabenz, imazapyr and imazaquin; nitriles, such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as, for example, mefenacet; sulfonylureas, such as, for example, amidosulfuron, bemsulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron-methyl and; thiocarbamates, such as, for example, butylate, cycloate, dialate, EPTCL, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as, for example, atrazine, cyanazine, simazine, simetrine, terbutryn and terbuthylazine; triazinones, such as, for example, hexazinon, metarnitron and metribuzin; others, such as, by

19 / 28 example, aminotriazole, benfuressate, bentazone, cinmethylin, clomazone, clopyralid, difenzoqual, dithiopyr, ethofumessate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulfodiphosphate, and trisulfodisulfate , flufenacet, foransulfuron, iodosulfuron methyl sodium, isoxadiphenethyl, isoxaflutol, mefenpyrdiethyl, mefenpyre methyl, mesosulfuron methyl, sulcotrione, mesotrione, prosulfuron, florassulam, clodinafop propargyl, pinodimxaden, trinexapacc-ethyl, dinexapacamide.

[0078] Examples of plant growth regulators that may be mentioned are chlorocholine chloride and ethephon.

[0079] Examples of repellents which may be mentioned are diethyl-toluamide, ethyl-hexane-diol and buto-pyronoxyl.

[0080] Other classes of pesticides that are suitable for formulation in the oily dithiocarbamate dispersions of the invention will be clearly understood by those skilled in the art or can be found, for example, in "The Pesticide Manual", 15th edition, The British Crop Protection Council, 2009 and the literature cited therein.

[0081] Examples of plant nutrients, which can be added to the oily dispersion of dithiocarbamate of the invention, are usual inorganic or organic fertilizers to supply plants with macro- and/or micronutrients, such as: ammonia salts, such as sulfate of ammonium, ammonium bisulfate, ammonium salts of carboxylic acids, ammonium chloride, ammonium carbonate, ammonium phosphate, urea and urea derivatives; phosphorus sources such as phosphoric salts (MAP monoammonium phosphate, DAP diammonium phosphate); potassium sources such as potassium phosphate and mono- or di-potassium carbonate; compounds containing micronutrients and secondary nutrients such as Zinc, Manganese, Magnesium, Iron, Calcium, Nickel, Molybdenum, Sulfur, Boron and their chelated salts; polycarboxylic acids such as citric acid; and mixtures thereof; derivatives

20 / 28 of protein and hydrolyzed proteins and mixtures thereof. Preferred plant nutrients are MAP, ammonium sulfate, sulfur, urea and urea derivatives.

[0082] The oil dispersion of dithiocarbamate of the invention may comprise from 0.01 to 5% by weight of a thickener to further improve the stability of the composition. Suitable thickeners are, for example, thickeners based on natural polymers such as cellulose derivatives; hydrogenated castor oil or polyhydroxystearic acid; bentones and modified silica. Natural oils and derivatives thereof are the preferred thickeners.

[0083] The oil dispersion according to the invention may comprise from 0.5 to 35% by weight of adjuvants commonly used in this field and well known to those skilled in the art, such as wetting agents, anti-caking agents, penetrants and adhesives.

[0084] In addition to each of the components mentioned above, said oil dispersion may also comprise from 0.1 to 10% by weight of other agronomic additives and "crop control" substances such as oil-soluble agrochemical active ingredients, carrier soluble in water and/or deflocculating agents (eg kaolin, lignin compounds), defoamers (eg silicon-based), antifreeze agents, dyes (eg azo dyes), preservatives (eg biocide and /or antioxidant), fillers, perfumes, evaporation inhibitors, pH modulators, etc.

[0085] The oil suspensions according to the invention can be prepared in a manner known per se.

[0086] In the method of the invention, the solid active ingredients are preferably used in the finely ground state, i.e. as a micronized powder of less than 50 microns in average size, preferably less than 20 microns, more preferably less than

21 / 28 that 10 microns or they can be reduced to this average particle size during any step of the preparation of the dispersion.

[0087] In one embodiment, it is possible to prepare the dispersion by first wet coarsely grinding and then wet finely grinding the active ingredient, in the presence of oil, so that the final mean particle size of the dithiocarbamate is below 50 microns , preferably below 20 microns. Grinding can be carried out in a colloid mill, ball mill, sand mill and preferably in grinding media mills.

[0088] In a further embodiment, it is possible to prepare the dispersion by mixing the oil, other possible liquid additives and solid ingredients that have been preliminarily pulverized to an average particle size of about 20 to 50 microns by a dry mill and then optionally subjecting the mixture to fine treatment by a wet mill, such as a ball mill or a sand mill, so that the final mean particle size of the dithiocarbamate is below 20 microns, preferably below 10 microns.

[0089] The described polyamide is preferably added after milling, but since it does not increase the viscosity of the dispersion of the invention, it can also be added before milling. It can be poured into the liquid as such, preferably heated to a temperature above 40°C or it can be pre-dispersed or pre-dissolved in the oil and then added to the crushed mixture.

The dithiocarbamate oil dispersions of the invention have a Brookfield RV® viscosity at 25°C and 20 rpm of at least 300 mPa*s, preferably at least 1000 mPa*s and usually below 25,000 mPa*s, preferably below 10,000 mPa*s.

[0091] The oily dispersion of dithiocarbamate can be diluted with water or aqueous solutions of agronomic compounds before use to produce a sprayable composition, which is used in plant treatment

22 / 28 or vintages. Dilution in water usually results in suspensions, emulsions, suspoemulsions or solutions of the dithiocarbamate in a concentration of at least 0.001 g/l. It may be advantageous to add, to the aqueous composition obtained, additional agrochemical active substances and/or adjuvants and additives conventionally used for application, for example adhesives or anti-caking agents.

[0092] The invention also relates to sprayable aqueous compositions obtained by diluting an oily dispersion of dithiocarbamate according to the present invention.

The invention also relates to a method which comprises applying to the plants or the locus thereof an effective amount of an aqueous sprayable composition obtained by diluting the oily dispersion of dithiocarbamate according to the present invention. Application can be done by crushing or aerial spraying equipment. The amount of active ingredient applied can vary within a relatively wide range. It essentially depends on the nature of the desired effect. In general, application rates are at least 0.01 g of active ingredient per hectare of soil surface.

EXAMPLES Characterization Methods

[0094] The acid number was determined following the standard ASTM method D1980-87.

The total amine value was determined following the ASTM standard method D2074-12.

Brookfield RV® viscosity (mPa*s) was determined at 25°C and 20 rpm using a Brookfield RV® viscometer. Ingredients

[0097] In the Examples the following ingredients were used: ● Fatty Acid Taloleum (TOFA);

23 / 28 ● Linolenic Acid; ● Diethylene Triamine (DETA); ● Triethylene Tetramine (TETA); ● Maleic Anhydride (MA); ● Citric Acid, anhydrous; ● Fumaric Acid; ● Mancozeb, 85% by weight of active substance; ● Metiram, 85% by weight of active substance; ● Maneb, 98% by weight of active substance; ● BANOLE, paraffin oil from Total SA; ● EDC 95/11, hydrocarbons, C15-C20, n-alkanes, isoalkanes, cyclics, < 0.03% aromatics, from Total SA; ● GENORA FLUID 9, paraffin oil from Total SA; ● Soy Lecithin; ● CHIMIPAL AC/9, ethoxylated fatty alcohol from Lamberti S.p.A.; ● EMULSON AG/CAL E, Alkylbenzene Sulphonate from Lamberti S.p.A.; ● ESATERGE 15 S5, alkoxylated fatty alcohol from Lamberti S.p.A.; ● AEROSIL 200, hydrophilic fumigated silica, from Evonik Resource Efficiency GMBH; ● FLUIDIFYER FD, polyester-based dispersant, by Lamberti S.p.A. Preparation of Polyamide Polyamide 1

[0098] 842.4 g of TOFA were charged into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical blade stirrer and heated to about 50°C. Afterwards 187.6 g of DETA were

24 / 28 added. The reaction mixture was further heated to 160°C under a nitrogen atmosphere and kept at this temperature for 3 hours. At the end of the reaction, the aminoamide acid number was below 10 mgKOH/g.

Subsequently, the dough was cooled to about 80°C and 151.4 g of MA was slowly added. The reaction temperature was increased to 180°C and maintained at this value for 60 min. The polyamide obtained had a total amine content below 26 mgKOH/g and an acid number of about 18 mgKOH/g.

The polyamide was then diluted in EDC 95/11 to a final concentration of 65% by weight based on the weight of the final solution. Polyamide 2

[00101] 650.2 g of TOFA were charged into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical blade stirrer and heated to about 50°C. Then 146.2 of THETA were added. The reaction mixture was further heated to 160°C under a nitrogen atmosphere and kept at this temperature for 3 hours. At the end of the reaction, the aminoamide had an acid number below 20 mgKOH/g.

[00102] Subsequently, the dough was cooled to about 90°C and 98.1 g of MA was slowly added. Reaction temperature maintained at 90°C for 60 minutes. The polyamide obtained had a total amine content below 50 mgKOH/g and an acid number below 45mgKOH/g.

The polyamide was then diluted in EDC 95/11 to a final concentration of 65% by weight based on the weight of the final solution. Polyamide 3

[00104] 578 g of TOFA were charged into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical blade stirrer and heated to about 50°C. Then 103.2 g of DETA was added. The reaction mixture was further heated to 160°C under a nitrogen atmosphere and kept at this temperature for 3 hours. In the end of

25 / 28 reaction, the aminoamide had an acid number below 20 mgKOH/g.

Subsequently, the mass was cooled to about 140°C and 192 g of Citric Acid was slowly added. The reaction temperature was increased to 160°C and maintained at this value for 60 minutes. The polyamide obtained had a total amine content below 20 mgKOH/g and an acid number of about 40 mgKOH/g.

The polyamide was then diluted in EDC 95/11 to a final concentration of 65% by weight based on the weight of the final solution. Polyamide 4

[00107] 578 g of TOFA were charged into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical blade stirrer and heated to about 50°C. Then 103.2 g of DETA was added. The reaction mixture was further heated to 160°C under a nitrogen atmosphere and kept at this temperature for 3 hours. At the end of the reaction, the aminoamide had an acid number below 20 mgKOH/g.

[00108] Subsequently, 116.1 g of Fumaric Acid was slowly added. The reaction temperature was increased to 180°C and maintained at this value for 120 minutes. The polyamide obtained had a total amine content below 20 mgKOH/g and an acid number of about 40 mgKOH/g and was liquid at room temperature.

[00109] The polyamide was then diluted in EDC 95/11, to a final concentration of 65% by weight based on the weight of the final solution. Polyamide 5

[00110] 314.1 g of linolenic acid were charged into a 1000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical blade stirrer and heated to about 50°C. Then 68.67 g of DETA was added. The reaction mixture was further heated to 155°C under a nitrogen atmosphere and held at this temperature for 3 hours. At the end of the reaction, the aminoamide acid number was below 20 mgKOH/g.

26 / 28

Subsequently, the dough was cooled to about 90°C and 65.3 g of MA was slowly added. The reaction temperature was increased to 165°C and maintained at this value for 90 min. The polyamide obtained had a total amine content below 50 mgKOH/g.

[00112] The polyamide was then diluted in EDC 95/11 to a final concentration of 65% by weight based on the weight of the final solution. Oil Dispersion Stability Test

[00113] The dithiocarbamate/oil mixtures were prepared by vigorously mixing the oil, the surfactants and the agrochemical active ingredient. The mixtures were milled with a ball mill until an optimal particle size distribution was achieved (D50 <2 µm; D90 <5 µm; determined with a Malvern Mastersizer 2000 laser light scattering spectrometer). The gram recipes for 100 grams of dithiocarbamate oil dispersions are summarized in Table 1. The stabilizers of the invention (Polyamides 1 to 5 ) and the comparative stabilizers (Aerosil 200 and Fluidifier FD), as such or pre-dissolved/pre-dispersed at a concentration of 25% by weight in the oil, were added to the various mixtures after milling.

[00114] All oily dispersions were homogeneous and showed no lumps or gels.

[00115] The stability test (storage stability test) was carried out at room temperature and at 54°C on each oil dispersion of dithiocarbamate in order to monitor over time the appearance of the dispersions, in particular the presence or absence of an oily or creamy phase in the composition, the presence or absence of aggregations or sediments, and the presence or absence of supernatants. For this purpose, about 100 ml of the agrochemical oil dispersions were sealed in glass containers and allowed to stand at room temperature (r.t.) and in an oven at 54°C. Table 2 reports the test results. "Thixotropic"

27 / 28 means that the dispersion has become noticeably more viscous, but is still flowable after stirring. “Gel” means that the dispersion has become extremely viscous and is no longer flowable, even after shaking. Table 1 Ingredient Ex. 1 Ex. 2 Ex. 3* Ex. 4* Ex. 5* Ex. 6* Ex. 7 Ex. 8 Ex. 9 Mancozeb 56 56 56 56 56 56 56 56 Metiram 20 Banol 30.25 64 35 33.0 30.25 30.25 30.25 Fluid Genera 9 30.25 30.25 Soy Lecithin 6 5.0 Chimipal AC/9 3 6.0 Esaterge 15 S5 13 15 13 13 13 13 13 Polyamide 1 0 .75 1.0 Polyamide 2 0.75 Polyamide 3 0.75 Polyamide 4 0.75 Aerosil 200 0.75 Fluidizer FD 0.75 * Comparative Table 2 Ingredient Ex. 10 Ex. 11 Ex. 12 Mancozeb 54.5 Metiram 54 .5 Maneb 54.5 Banol 31.75 31.75 31.75 Esaterge 15 S5 13 13 13 Polyamide 1 0.75 0.75 Polyamide 5 0.75 Table 3 Viscosity RV Appearance (7 Appearance (60 Appearance Example Brookfield Appearance) days rt) days rt) (14 days 54°C) 1 Fluid 3970 Fluid Thixotropic Fluid 2 Fluid 2900 Thixotropic Fluid Thixotropic 3* Fluid 3400 Thixotropic Fluid Gel 4* Fluid 3250 Thixotropic Fluid Gel 5* Fluid 3600 Gel Gel Gel 6* Fluid 3800 Gel Gel Gel 7 3800 Fluid Thixotropic Fluid 8 Tixotropic Fluid 3700 Thixotropic Fluid 9 F Thixotropic fluid 3750 thixotropic fluid thixotropic 10 fluid 3000 thixotropic fluid thixotropic 11 fluid 2800 thixotropic fluid thixotropic 12 fluid 3300 thixotropic fluid thixotropic * Comparative

[00116] The results demonstrate that the polyamides of the invention do not increase the viscosity of the oily dispersions, do not form gels or lumps on dissolution and have very good stabilizing performances.

[00117] Oily dispersions of dithiocarbamate according to

The invention can be easily prepared and show good stability over time, also at elevated temperatures.

These dispersions are pourable, even after long storage, dispersible in water using minimal agitation, and have very little tendency to form films in water, which can easily clog nozzle sieves.

Claims (10)

1. Oily dispersion of dithiocarbamate, characterized in that it comprises: from 5.0 to 60 by weight (% by weight) of at least one fungicide of the dithiocarbamates family, from 10 to 90% by weight of an oil and from 0 .05 to 10% by weight of a polyamide obtained by reacting in a first step: a) one mole of a polyamine having n amino groups with exchangeable hydrogens, where n is an integer ranging from 3 to 4 with b) from 1 to n-1 mol of a saturated or unsaturated C6–C30 aliphatic monocarboxylic acid or an ester thereof; to obtain an aminoamide having an acid number below 30 mgKOH/g and subsequently reacting the remaining amino groups carrying exchangeable hydrogens of the aminoamide with: c) from 0.3 to 1.0 mol of a di- and/or tricarboxylic acid C2-C10 or the corresponding anhydride for each mole of amino groups remaining; to obtain a polyamide with a total amine value below 60 mgKOH/g. 2. Oily dispersion of dithiocarbamate according to claim 1, characterized in that it comprises: from 7 to 60% by weight of at least one fungicide of the dithiocarbamates family; from 20 to 80% by weight of an oil and from 0.1 to 5.0% by weight of said polyamide. 3. Dithiocarbamate oily dispersion according to claim 1, characterized in that said polyamine a) is a polyalkylene polyamine of the formula I: H2N[(CH2)xNH]yH I where x is an integer ranging from 1 to 6 and y is an integer ranging from 2 to 3. 4. Oily dithiocarbamate dispersion according to claim 3, characterized in that said polyamine a) is a polyalkylene polyamine of formula I in which x is 2, that is, a polyethylene amine. 5. Oily dispersion of dithiocarbamate according to claim 1, characterized in that the saturated or unsaturated aliphatic C6–C30 monocarboxylic acid b) is a mixture of saturated or unsaturated aliphatic C12–C22 monocarboxylic acids. 6. Oily dispersion of dithiocarbamate according to claim 1, characterized in that the di or tricarboxylic acid C2-C10 c) is a dicarboxylic acid C3-C8. 7. Oily dispersion of dithiocarbamate according to claim 1, characterized in that said oil is selected from the group consisting of linear or branched C8 to C30 paraffins having boiling points above 140°C (paraffin oils); mineral oil; C7 to C18 aromatic or cycloaliphatic hydrocarbon compounds; vegetable oils or transesterification products thereof; animal oils; liquid esters of C1 to C12 monoalcohols with C2 to C10 carboxylic or polycarboxylic acids; liquid amides of C1 to C5 alkylamines or alkanolamines amines with C6 to C18 carboxylic acids; and mixtures thereof. 8. Dithiocarbamate oily dispersion according to claim 7, characterized in that the oil is chosen from paraffin oils, mineral oils, vegetable oils or products of their transesterification and mixtures thereof. 9. Oily dispersion of dithiocarbamate according to claim 1, characterized in that it additionally comprises from 5 to 30% by weight of at least one surfactant. 10. Method for treating plants, crops or fields, characterized by the fact that it comprises the steps of: i. providing an oil dispersion of dithiocarbamate according to claims 1 to 9; ii. diluting said oily dispersion of dithiocarbamate with water or an aqueous solution of agronomic compounds to produce a sprayable composition; iii. applying to plants, crops or fields an effective amount of said sprayable aqueous composition.