An oil-in-water emulsion-based agrochemical formulation

Abstract

A oil-in-water emulsion-based agrochemical formulation comprises i) an oil-phase component comprising one or more agrochemical active ingredient(s) dissolved in a water-immiscible solvent or solvent mixture, and ii) a water-phase component, iii) a pickering emulsifier, obtainable by radical aqueous emulsion polymerization of a mixture comprising a) ethylenically unsaturated monomers M, with M comprising at least one vinyl ester M1, and at least one (meth)acrylic acid ester M2, b) a carboxyl-groups-containing compound CGCC, c) at least one non-carboxylated saccharide and / or polysaccharide S, and d) at least one emulsifier selected from non-ionic and anionic surfactants, wherein the dispersion has a pH of up to 4. The oil-in-water emulsion-based agrochemical formulation exhibits an outstanding performance as a pickering emulsifier.

Description

[0001] An Oil-in-Water Emulsion-Based Agrochemical Formulation

[0002] Field of the Invention

[0003] The present invention is directed to an oil-in-water emulsion-based agrochemical formulation; and to the use of an aqueous polymer dispersion as a pickering emulsifier in an oil-in-water emulsion.

[0004] Background to the Invention

[0005] When preparing agrochemical formulations, it is usually required to dissolve the agrochemically active ingredient, e.g. one or more pesticides in a solvent, which is then diluted in a larger volume of water in order for it to be applied in the form of a fine spray. In the case of active ingredients that are not water-soluble, it is normally necessary to dissolve the formulation in a water-immiscible solvent and add one or more surfactants, so that the solution will form an oil-in-water emulsion, when added to water. Such a formulation is called an Emulsifiable Concentrate (EC) formulation. Alternatively, the water-immiscible solution comprising active ingredient can be pre-emulsified in water in a concentrated form. Such a formulation is called an Emulsion-in-water (EW) formulation.

[0006] Traditional emulsions are stabilized by small molecule surfactants, which is a meta-stable system dynamically stable, but thermodynamically unstable. Compared with traditional emulsions, pickering emulsions have better stability, antiaggregation and anti-flocculation abilities. Solid particles playing an emulsifying effect are irreversibly adsorbed on a water-oil interphase. There is an urgent need to reduce the introduction of (micro)plastic into the environment, to be more precise of (micro)plastic which is not or not readily biodegradable.

[0007] It is an object of the present invention to provide a oil-in-water emulsion-based agrochemical formulation which relies on pickering particles that are biodegradable.

[0008] Summary of the Invention

[0009] The present invention relates to an oil-in-water emulsion-based agrochemical formulation comprising:

[0010] I) an oil-phase component comprising one or more agrochemical active ingredient(s) dissolved in a water-immiscible solvent or solvent mixture, and

[0011] II) a water-phase component, ill) a pickering emulsifier, obtainable by radical aqueous emulsion polymerization of a mixture comprising a) ethylenically unsaturated monomers M, with M comprising

[0012] (1) at least one vinyl ester M1 , preferably comprising vinyl acetate, more preferably comprising vinyl acetate at least 50%, and

[0013] (2) at least one (meth)acrylic acid ester M2 optionally comprising methacrylic acid as minor component, the (meth)acrylic acid in the methacrylic acid ester being bonded via an ether-function to a polyalkylene oxide- derived-block PAO, wherein the PAO consists of 2 to 40 alkylene oxide AO-units, most preferably 25 AO- units, with the PAO preferably being further linked via an ether-function to an C1 to 024, preferably at least 04, more preferably at least 06, even more preferably 08 to 024-aliphatic alkanol, most preferably a 018- aliphatic alkanol, with the AO being preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50, more preferably at least 75, even more preferably at least 90 wt.% most preferably essentially only EO, based on total AO; preferably comprising methacrylic acid, more preferably with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%;

[0014] (3) optionally further monomers M3 polymerizable with M1 and M2, preferably none; b) 1 to 15, preferably 2 to 10%, based on the total weight of monomers M, of a carboxyl-groups-containing compound CGCC being selected from a compound bearing in its structure at least three carboxyl -groups of which at least 10 and at most 90 percent are being deprotonated, selected from the group comprising citric acid, isocitric acid; ethylendiamintetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acid; oligomeric and poly methacrylic acid; trimelitic acid; oligomeric aminoacids with carboxy groups such as polyaspartic acid; oligomeric and polyglutaminic acid; oligomeric and polyacetates with carboxygroups such as poly (glyoxalic)aldehyde; carboxylated oligomeric and polymeric saccharides such as oxidized starch (mixtures of amylopektines, amylose); polyglucuronates; cellulose oxidized to cellouronate; natural polycarboxylatic polysaccharide such as xylanes; pektines acid; alginic acid; carboxy methylated polysaccharides based on 1 ,4- polyglucanes, 1 ,3-polyglucanes, 1 ,6-polyglucanes; Poly-uronic acids based on 1 ,4-polyglucanes, 1 ,3- polyglucanes, 1 ,6-polyglucanes; polygalacturonic; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC”); c) at least one non-carboxylated saccharide and / or polysaccharide S, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35wt% based on the total weight of monomers M; d) at least one emulsifier selected from non-ionic and anionic surfactants; e) optionally sulfate ions; and f) optionally sulfite ions; wherein - preferably - the amount of M1 is from 80 to 99,99 mol%, and the amount of M2 is from 0,01 to 20 mole%, and preferably at most 10, even more preferably at most 5, more preferably at most 2%, the total amount of M1 plus M2 being 100 weight percent, and wherein the dispersion has - after the end of the polymerization - a pH of up to 4.

[0015] Surprisingly, it has been found that an aqueous polymer dispersion, obtainable by radical aqueous emulsion polymerization as described above exhibits an outstanding performance as a pickering emulsifier.

[0016] The invention further relates to the use of an aqueous polymer dispersion as defined above as a pickering emulsifier in an oil-in-water emulsion. Definitions

[0017] An emulsion is a mixture of two or more liquids that are normally immiscible, wherein one liquid forms a dispersed phase, suspended as tiny droplets within the other liquid, which is known as the continuous phase. Emulsions are typically referred to as oil-in-water (i.e. the water is the continuous phase) or water-in-oil (i.e. the oil is the continuous phase). In the context of agrochemical formulations, oil-in-water emulsions, known as emulsion-in-water formulations are often used to disperse hydrophobic pesticides across fields of crop plants.

[0018] In the present invention, an "active ingredient” is a compound which directly exerts a biologically relevant effect, preferably a pesticidal effect as described herein. The U.S Environmental Protection Agency (EPA) defines a pesticide as "any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest". A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the context of agrochemical formulations, pesticides are used to actively target pests, typically fungi, insects, and / or weed plants, without unduly harming the crop plant.

[0019] Unless indicated otherwise, all amounts in % by weight refer to the weight of the total agrochemical formulation.

[0020] The pH value is determined at room temperature (23 °C) and atmospheric pressure.

[0021] Detailed Description

[0022] In a first aspect, the present invention is directed to an oil-in-water emulsion-based agrochemical formulation comprising:

[0023] I) an oil-phase component comprising one or more agrochemical active ingredient(s) dissolved in a water-immiscible solvent or solvent mixture, and

[0024] II) a water-phase component, ill) a pickering emulsifier, obtainable by radical aqueous emulsion polymerization as described above.

[0025] The pickering emulsifier is obtainable in the form of an aqueous polymer dispersion by radical aqueous emulsion polymerization of a mixture comprising a) ethylenically unsaturated monomers M, with M comprising

[0026] (1) at least one vinyl ester M1 , preferably comprising vinyl acetate, more preferably comprising vinyl acetate at least 50%, even more preferably at least 90%, and

[0027] (2) at least one (meth)acrylic acid ester M2 optionally comprising meth-acrylic acid as minor component, the (meth)acrylic acid in the meth-acrylic acid ester being bonded via an ether-function to a polyalkylene oxide- derived-block PAO, wherein the PAO consists of 2 to 40 alkylene oxide AO, most preferably 25 AO-units, with the PAO preferably being further linked via an ether-function to an C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, most preferably a C18-aliphatic alkanol, with the AO being preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50, more preferably at least 75, even more preferably at least 90 wt.% most preferably essentially only EO, based on total AO; preferably comprising methacrylic acid, more preferably with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%;

[0028] (3) optionally further monomers polymerizable with M1 and M2, preferably none; b) 1 to 15, preferably 2 to 10, more preferably 3 to 8, most preferably 4 to 6% by weight, based on the total weight of monomers M, of a carboxyl-groups-containing compound CGCC being selected from a compound bearing in its structure at least three, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl-groups of which at least 10 and at most 90 percent are being deprotonated (thus forming salts with counter-ions; the counter-ions being selected from Na, K, NH4, Mg, Ca), selected from the group comprising citric acid, isocitric acid; ethylendiamintetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and poly-acrylic acid; oligomeric and poly methacrylic acid; trimelitic acid; oligomeric aminoacids with carboxy groups such as polyaspartic acid; oligomeric and poly-glutaminic acid; oligomeric and polyacetates with carboxygroups such as poly(glyoxalic)aldehyde; carboxylated oligomeric and polymeric saccharides such as oxidized starch (mixtures of amylopektines, amylose); polyglucuronates; cellulose oxidized to cellouronate; natural polycarboxylatic polysaccharide such as xylanes; pektines acid; alginic acid; carboxymethylated polysaccharides based on 1 ,4-polyglucanes, 1 ,3-polyglucanes, 1 ,6- polyglucanes; Poly-uronic acids based on 1 ,4-polyglucanes, 1 ,3-polyglucanes, 1 ,6-polyglucanes; polygalacturonic; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC”); and c) at least one (non-carboxylated) sacharide and / or polysaccharide S, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35, more preferably 10 to 30, most preferably 15 to 25 wt% based on the total weight of monomers M, d) at least one emulsifier selected from non-ionic and anionic surfactants, with

[0029] I) the at least one anionic surfactant preferably being selected from: anionic emulsifier bearing at least one anionic group, which is selected from phosphate, phosphonate, sulfate and sulfonate groups; the anionic emulsifier typically employed in the form of their alkali metal salts, especially of their sodium salts or in the form of their ammonium salts; preferably the anionic emulsifier bearing at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably bearing at least one sulfonate or sulfate group, most preferably only one sulfonate or one sulfate group, i-a) with the anionic emulsifier bearing at least one sulfate or sulfonate group preferably being selected from

[0030] - the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C8-C22-alkyl sulfates, - the salts, especially the alkali metal and ammonium salts, of sulfuric monoesters of C2-C3-alkoxylated alkanols, especially of sulfuric monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an 02- C3-alkoxylation level (AO level) in the range from 2 to 40,

[0031] - the salts, especially the alkali metal and ammonium salts, of sulfuric monoesters of C2-C3-alkoxylated alkylphenols, especially of sulfuric monoesters of C2-C3-alkoxylated C4 018-alkylphenols (AO level preferably 3 to 40),

[0032] - the salts, especially the alkali metal and ammonium salts, of alkyl-sulfonic acids, especially of 08-022- alkylsulfonic acids,

[0033] - the salts, especially the alkali metal and ammonium salts, of dialkyl esters, especially di-C4-C18-alkyl esters of sulfosuccinic acid,

[0034] - the salts, especially the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, especially of 04- 022-alkylbenzenesulfonic acids, and

[0035] - the salts, especially the alkali metal and ammonium salts, of mono- or disulfonated, alkyl-substituted diphenyl ethers, for example of bis(pheny Isulfonic acid) ethers bearing a 04-024-al ky I group on one or both aromatic rings; with the term "C2-C3-alkoxylated” meaning that the compounds are ethoxylated, propoxylated or co- ethoxylated / propoxylated, i.e. meaning that the respective compounds are obtained by a process which introduces a poly-ethylenoxide group, a polypropyleneoxide group or a poly(ethyleneoxide-co-propyleneoxide) group; i-b) With the anionic emulsifier bearing at least one phosphate or phosphonate group, preferably being selected from

[0036] - the salts, especially the alkali metal and ammonium salts, of mono- and dialkyl phosphates, especially 08- 022-alkyl phosphates,

[0037] - the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30, for example phosphoric monoesters of ethoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric monoesters of propoxylated C8-C22-alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and phosphoric monoesters of ethoxylated-co-propoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,

[0038] - the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of C2-C3-alkoxylated alkylphenols, especially phosphoric monoesters of C2-C3-alkoxylated 04-018-alkylphenols (AO level preferably 3 to 40),

[0039] - the salts, especially the alkali metal and ammonium salts, of alkylphosphonic acids, especially 08-022- alkylphosphonic acids and

[0040] - the salts, especially the alkali metal and ammonium salts, of alkylbenzenephosphonic acids, especially 04- 022-alkylbenzenephosphonic acids; with the more preferred anionic emulsifiers being selected from the following groups:

[0041] - the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C8-C22-alkyl sulfates,

[0042] - the salts, especially the alkali metal salts, of sulfuric monoesters of C2-C3-alkoxylated alkanols, especially of sulfuric monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40,

[0043] - of sulfuric monoesters of C2-C3-alkoxylated alkylphenols, especially of sulfuric monoesters of C2-C3- alkoxylated C4-C18-alkylphenols (AO level preferably 3 to 40),

[0044] - of alkylbenzenesulfonic acids, especially of C4-C22-alkylbenzenesulfonic acids, and

[0045] - of mono- or disulfonated, alkyl-substituted diphenyl ethers, for example of bis(phenylsulfonic acid) ethers bearing a C4-C24-alky I group on one or both aromatic rings; ii) the at least one non-ionic surfactant being selected from: nonionic emulsifiers are e.g. ar-aliphatic or aliphatic nonionic emulsifiers, selected from

[0046] - C2-C3-alkoxylated mono-, di- and trialkylphenols, with the number of repeating units of the alkylene oxidederived moiety being preferably 3 to 50, and / or the alkyl radical being preferably C4-C10-alkyl;

[0047] - C2-C3-alkyoxlates, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, of long-chain alcohols with the number of repeating units of the alkylene oxide-derived moiety being preferably 3 to 100, and / or the alkyl radical being preferably C8-C36-alkyl, and

[0048] - polyethylene oxide / polypropylene oxide homo- and copolymers, which may comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homo-blocks and randomblocks, more preferably C2-C3-alkoxylated of long-chain alkanols, in particular to those where the alkyl radical C8 C30 having a mean alkoxylation level of 5 to 100 and, among these, particular preference to those having a linear C12-C20 alkyl radical and a mean alkoxylation level of 10 to 50, and also to C2-C3-alkoxylated monoalkylphenols; e) optionally sulfate ions, and f) optionally sulfite ions, wherein - preferably - the amount of M1 is from 80 to 99.99 mol%, more preferably the amount of M1 being at least 98%, and the amount of M2 is from 0.01 to 20 mole%, more preferably from 0.1 , even more preferably from 0.2, even more preferably from 0.5, and most preferably from 0.7, and preferably at most 10, even more preferably at most 5, more preferably at most 2%, and most preferably the amount of M1 being about 99 weight percent and the amount of M2 being about 1 weight percent, the total amount of M1 plus M2 being 100 weight percent, and wherein the dispersion has - after the end of the polymerization - a pH of up to 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6, and more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, and most preferably at least 3.4.

[0049] In a preferred embodiment, the vinyl ester M1 monomer comprises vinyl acetate with at least 50%, even more preferably at least 90% based on the total molar amount of vinyl esters.

[0050] In another preferred embodiment, the least one (meth)acrylic acid ester M2 is a (meth)acrylic acid being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 20 to 30 alkylene oxide AO, most preferably 25 AO-units, with the PAO preferably being further linked via an ether-function to an C14 to 022 - aliphatic alkanol, most preferably a 016 / 18-aliphatic alkanol, with the AO being selected from EO and PO and / or BuO, more preferably EO and PO, with the EO in an amount of from 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on total AO; further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%.

[0051] In a further preferred embodiment, M3 is not comprised.

[0052] In an even more preferred embodiment, in the aqueous polymer dispersion as defined before, the vinyl ester M1 monomer comprises vinyl acetate with at least 50%, even more preferably at least 90% based on the total molar amount of vinyl esters, the least one (meth)acrylic acid ester M2 is a (meth)acrylic acid being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 20 to 30 alkylene oxide AO, most preferably 25 AO-units, with the PAO preferably being further linked via an ether-function to an 014 to 022 -aliphatic alkanol, most preferably a 016 / 18-aliphatic alkanol, with the AO being selected from EO and PO and / or BuO, more preferably EO and PO, with the EO in an amount of from 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on total AO; further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%, and M3 is not comprised.

[0053] In a further more preferred embodiment, the vinyl ester M1 monomer comprises vinyl acetate with at least 90% based on the total molar amount of vinyl esters, preferably essentially only vinyl acetate, and the least one (meth)acrylic acid ester M2 is a (meth)acrylic acid being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 23 to 27 alkylene oxide AO, most preferably on average 25 AO-units, with the PAO preferably being further linked via an ether-function to essentially 016 / 18 -aliphatic alkanol, most preferably a 016 / 18-aliphatic alkanol, with the AO being essentially only EO; further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%, and M3 is not present. In a further more preferred embodiment, M1 is vinyl acetate, and the least one (meth)acrylic acid ester M2 is a methacrylic acid being bonded via an ether-function to a polyethylene oxide block PEO, wherein the PEO consists of on average 25 AO-units, with the PEO being further linked via an ether-function to a C16 / 18-aliphatic alkanol, further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of about 75 w% / 25w%, and M3 is not present.

[0054] In a further more preferred embodiment, and preferably in combination with any of the embodiments before, the aqueous dispersion comprises as the CGCC a carboxyl-groups-containing compound being selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC”), preferably in amounts of from 1 weight % up to 15 weight percent, more preferably up to 10, even more preferably up to 5 wt% and most preferably about 5 weight percent based on the total amount of monomers M1+M2+M3.

[0055] It is believed that the CGCC is able to interact with the polymerized moiety derived from the at least one monomer M2 within the polymer product which is dispersed within the dispersion. By such interaction, an excellent compatibility and stability of the dispersion seems to result; also, such interactions favors the attack at the chemical structure and thus provides the high biodegradation percentage of the aqueous polymer dispersion observed, which is higher than dispersions not containing a carboxyl-groups-containing compound CGCC.

[0056] In one further preferred embodiment, and preferably in combination with any of the embodiments before, the aqueous polymer dispersion comprises at least one saccharide and / or polysaccharide S which is a starch degradation product, preferably a maltodextrin, in an amount of 10 to 30, most preferably 15 to 25 wt% based on the total weight of monomers M.

[0057] In a preferred embodiment, S is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range from 2 to 40%.

[0058] In a preferred embodiment, S is maltodextrin with a DE-value of from 10 to 30, preferably 12 to 16 or 25 to 30.

[0059] In a preferred embodiment, S is a degraded starch having a number average molecular weight in the range from 300 to 2000 Dalton, as determined by osmometry, and preferably in a range of from 5 to 150, more preferably up to 70, even more preferably up to 50, and more preferably from 10, even more preferably from 15, and most preferably from 20, each in weight percent based on the total weight of monomers M1+M2+M3.

[0060] Such degraded starches can be obtained by known means, such as chemical degradation, catalytic degradation with suitable catalysts or using enzymes. It is preferred herein, that S stems from an enzymatic degradation as this is a clean and fast approach with basically no chemical residues from the degradation reaction within the degradation products (besides starch and sugars from the starch).

[0061] The use of maltodextrin additionally provides an increased stability at lower temperature of storage for the inventive dispersions.

[0062] Preferably, the dispersed polymer particles of the aqueous polymer dispersions of this invention have a D[4,3] value as determined by static light scattering of 100 to 1000 nm, preferably 100 to 700 nm, more preferably 100 to 500 nm.

[0063] The aqueous polymer dispersions of any of the embodiments disclosed herein preferably have at least one of the following properties a) to d), preferably at least two, more preferably at least three, and most preferably all of the hereinafter defined properties: a) a transmittance of 532nm-wavelength-light of at least 20% when measured as a 0.01wt% dispersion in water, b) a pH of in between 2.5 and 9, preferably from 3, more preferably from 3.3, and more preferably up to 7, even more preferably up to 6, even more preferably up to 5, and most preferably about 3.5; c) a density of from 1.04 to 1.08 g / mL measured as 10wt.%-dispersion (based on solid content), and d) a viscosity of from 30 to 1000 mPas (Brookfield viscosity, spindle 3; measured as 30 wt.%-dispersion containing 30 wt.% active (active = polymer plus CGCC plus S); based on solid content; concentration as applicable by measurement).

[0064] The aqueous polymer dispersions used herein may be obtained, e.g., in large-scale production, by a process comprising:

[0065] (A) polymerizing ethylenically unsaturated monomers M, with M comprising at least one vinyl ester M1 , preferably comprising vinyl acetate, more preferably comprising vinyl acetate at least 50%, even more preferably at least 90%, and at least one (meth)acrylic acid ester M2, optionally comprising meth-acrylic acid as minor component, the (meth)acrylic acid in the meth-acrylic acid ester being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 2 to 40 alkylene oxide AO, most preferably 25 AO-units, with the PAO preferably being further linked via an ether-function to an C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, most preferably a C18-aliphatic alkanol, with the AO being preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50, more preferably at least 75, even more preferably at least 90 wt.% most preferably essentially only EO, based on total AO; preferably comprising methacrylic acid, more preferably with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%; and optionally further monomers M3 polymerizable with M1 and M2, preferably none; in the presence of

[0066] - at least one emulsifier,

[0067] - water, - 1 to 15, preferably 2 to 10, more preferably 3 to 8, most preferably 4 to 6% by weight, based on the total weight of monomers M, of a carboxyl-groups-containing compound CGCC being selected from a compound bearing in its structure at least three, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl-groups of which at least 10 and at most 90 percent are being deprotonated (thus forming salts with counter-ions; the counter-ions being selected from Na, K, NH4, Mg, Ca), selected from the group comprising citric acid, isocitric acid; ethylendiamintetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acid; oligomeric and poly methacrylic acid; trimelitic acid; oligomeric aminoacids with carboxy groups such as polyaspartic acid; oligomeric and poly-glutaminic acid; oligomeric and polyacetates with carboxygroups such as poly(glyoxalic)aldehyde; carboxylated oligomeric and polymeric saccharides such as oxidized starch (mixtures of amylopektines, amylose); polyglucuronates; cellulose oxidized to cellouronate; natural polycarboxylatic polysaccharide such as xylanes; pektines acid; alginic acid; carboxymethylated polysaccharides based on 1 ,4-polyglucanes, 1 ,3-polyglucanes, 1 ,6- polyglucanes; poly-uronic acids based on 1 ,4-polyglucanes, 1 ,3-polyglucanes, 1 ,6-polyglucanes; polygalacturonic; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC”); and

[0068] - at least one (non-carboxylated) saccharide and / or polysaccharide S, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35, more preferably 10 to 30, most preferably 15 to 25 wt% based on the total weight of monomers M, with the use of at least one radical initiator or a radical initiator couple, such couple preferably comprising a peroxide and a reducing compound; such polymerization being performed

[0069] - in a reaction container equipped with either pressurized equipment and / or equipment to control boiling of the ingredients and with such measure(s) being able to contain the ingredients within the reaction container during the reaction at elevated temperature;

[0070] - at a temperature of from 60 to 90, preferably 70 to 80 °C;

[0071] - at a pH of up to 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6; with

[0072] (B) optionally adding further radical initiator or initiator couple to further reduce the content of the unreacted monomers and / or to reduce the color of the to be obtained polymer dispersion;

[0073] (C) optionally adding at least one further reducing compound to reduce the color of the to be obtained polymer dispersion,

[0074] (D) optionally adding at least one further additive that might be needed or desired as additional ingredient within the to be obtained polymer dispersion;

[0075] (E) optionally performing a step of removing evaporable compounds from the reaction mixture by employing a distillation step and / or a stripping step using steam or a gas, preferably steam;

[0076] (F) optionally performing a step of filtrating the polymer dispersion from the previous step, preferably using a 125 micrometer filter; to obtain the aqueous polymer dispersion. As a result of the polymerization reaction, the aqueous dispersion may contain sulfite and / or sulfate ions. Those arise mainly from the use of persulfate-radical initiators.

[0077] During the polymerization, the pH-value of the mixture typically decreases due to the formation of acid from the use of the persulfate-initiators. In principle, this decrease of pH can be minimized by adding a base. However, the use of a base is not preferred. The amount of coagulates typically increases the more base is added as the amount of electrolytes increases.

[0078] In preferred embodiment, for the main polymerization step at least one persulfate as radical polymerization initiator and ascorbic acid and / or iso-ascorbic acid are employed.

[0079] In preferred embodiment, and preferably in combination with any of the embodiments before, the radical polymerization initiator additionally comprises a transition metal, preferably an iron-containing salt. In the most preferred embodiment, no transition metal is employed. Iron-containing salt are typically complexes of iron-cations, such as complexes with EDTA and the like. Such complexes are known for such applications in combination with persulfate-radical initiators.

[0080] In preferred embodiment, and preferably in combination with any of the embodiments before, in the post polymerization step at least one hydroperoxide and at least one sulfite salt are employed.

[0081] In preferred embodiment, and preferably in combination with any of the embodiments before, at least 5% of the total amount of the hydroperoxide being added in the post polymerization step is added after the end of the addition of the sulfite.

[0082] In preferred embodiment, and preferably in combination with any of the embodiments before, volatile components are removed using steam distillation, thermal distillation, vacuum distillation, gas stripping, to reduce and preferably essentially remove remaining amounts of monomer(s) M1 , and reaction by-products, to a level which is a required level or an acceptable level for the intended area of application, such step being performed at ambient, reduced or overpressure of at most 2 bar absolute pressure, to reduce the content of the organic solvent(s), residual volatile monomers such as vinyl esters, to a content of at most 1 weight percent, preferably at most 0.5, more preferably at most 0.01 percent, based on the total weight of the polymer dispersion obtained.

[0083] In preferred embodiment, and preferably in combination with any of the embodiments before, the dispersion finally obtained after the last process step to polymerize and - if employed - to purify is filtered to remove polymer agglomerates of sizes beyond 125 micrometer.

[0084] The aqueous polymer dispersion is suitably biodegradable. Biodegradable materials are broken down by microorganisms, generally in the presence of oxygen (aerobic decomposition), to carbon dioxide, water, biomass and minerals. Biodegradability in terms of the present invention is as determined with one of the methods defined by the European Chemicals Agency (ECHA) in the "Background Document to RAC and SEAC Opinions on Intentionally Added Microplastics'' of 11 June 2020, section 2.2.1.6, table 22.

[0085] The (i) oil-phase component comprises one or more agrochemical active ingredient(s) dissolved in a water-immiscible solvent or solvent mixture.

[0086] Water-immiscible solvent or solvent mixture

[0087] Herein, "water-immiscible” solvent denotes that the solvent is not completely miscible with water. Preferably, the water- immiscible solvent comprises at least one solvent having a water solubility of less than or equal to 1 .5% w / w, preferably less than or equal to 1 .0% w / w, more preferably less than or equal to 0.5% w / w. In an embodiment, the water-immiscible solvent comprises exclusively solvents having a water solubility of less than or equal to 1 .5% w / w.

[0088] The solvent is not subject to particular limitations and may be any solvent conventionally used in oil-in-water emulsionbased agrochemical formulations. Suitable solvents include hydrocarbons, vegetable oils, amide solvents, ester solvents, carbamate-based solvents, and mixtures thereof.

[0089] Hydrocarbon solvents

[0090] Suitable hydrocarbon solvents comprise aromatic hydrocarbons such as benzene, toluene, xylene; and paraffinic mineral oils.

[0091] Amide solvents

[0092] Preferably, at least one of the one or more amide solvents, more preferably each of the one or more amide solvent, has from 7 to 20 carbon atoms, more preferably from 9 to 17 carbon atoms, most preferably from 11 to 15 carbon atoms.

[0093] In a particularly preferred embodiment, the one or more amide solvents are selected from the group consisting of dimethyl hexanamide, dimethyl heptanamide, dimethyl octanamide, dimethyl nonanamide, dimethyl decanamide, dimethyl undecanamide, dimethyl dodecanamide, dimethyl tridecanamide, dimethyl tetradecanamide, dimethyl pentadecanamide, dimethyl hexadecanamide, dimethyl heptadecanamide, dimethyl octadecanamide, dimethyl nonadecanamide, dimethyl icosanamide and unsaturated variants thereof, such as dimethyl soyate amide, dimethyl canolate amide and dimethyl oleanamide, as well as fatty acid dimethylamide mixtures, such as Ce-C fatty acid dimethylamide and C12-C18 fatty acid dimethylamide, and combinations of any of the above. Ester solvents

[0094] Preferably, at least one of the one or more ester solvents, more preferably each of the one or more ester solvents, has from 2 to 25 carbon atoms, more preferably from 4 to 22 carbon atoms, most preferably from 7 to 20 carbon atoms.

[0095] In a particularly preferred embodiment, the one or more ester solvents are selected from the group consisting of methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl dodecanoate, methyl tridecanoate, methyl tetradecanoate, methyl pentadecanoate, methyl hexadecanoate, methyl heptadecanoate, methyl octadecanoate, methyl nonadecanoate, methyl icosanoate, methyl isononoate, 1 -ethylhexyl palimatate, caprylic / capric triglyceride, propylene glycol dicaprylate / dicaprate, Propane-1 , 2, 3-triyl 2-ethy I hexanoate, 2,2-bis[(octanoyloxy)methyl]butyl decanoate, Trimethylolpropane trioleate, 2 -ethylhexyl acetate, dibutyl adipate, and 2-ethy lhexy I cocoate, and unsaturated variants thereof, such as methyl soyate ester, methyl canolate ester and methyl oleate, as well as fatty acid methyl ester mixtures, such as Ce-C fatty acid methyl ester and C12-C18 fatty acid methyl ester, and combinations of any of the above.

[0096] Carbamate-based solvents

[0097] Suitable carbamate-based solvent are selected from at least one compound of the following list:

[0098] In addition to the above-mentioned solvents, co-solvents may be incorporated in the solvent mixture. The co-solvent may have a water solubility of greater than 1 .50% w / w. Suitable co-solvents may be selected from propylene carbonate, butylene carbonate, glycerine carbonate, hexyl glycol, hexylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, triethylene glycol, butyl glycol, butyldiglycol, butoxypropan-2-ol, dipropylene glycol monobutyl ether, 2,2,4-trimethyl-l ,3-pentanediol, di(ethylene glycol)monomethyl ether, di(ethylene glycol)ethyl ether, di(ethylene glycol)monopropyl ether, 3-methoxy-3-methyl-1 -butanol, methoxy propanol, N,N-dimethyl lactamide, ethyl lactate, propyl lactate, butyl lactate, cyclohexanone, benzyl alcohol, triethyl citrate, gamma butyrolactone, gamma caprolactone, methyl levulinate, ethyl levulinate, 1 ,2-isopropylidengylcerol (solketal), glycerinformal, n-methyl pyrrolidone, n-ethyl pyrrolidone, n-butyl pyrrolidone, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethylacetoacetamide, diethylacetoacetamide, dimethylisosorbide, dihydrolevoglucosenone, methyl acetoacetate, ethyl acetoacetate, dimethyl 3-methylglutarate and combinations of any of the above.

[0099] Agrochemical active ingredient(s)

[0100] The agrochemical active ingredient is not subject to particular limitations and may be any agrochemical active ingredient conventionally used in oil-in-water emulsion-based agrochemical formulations. In an embodiment, the agrochemical active ingredient is a pesticide, preferably selected from an insecticide, a herbicide, a fungicide, and combinations thereof.

[0101] A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term "pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.

[0102] The following lists of pesticides that are suitable for use in the agrochemical formulations of the invention, is intended to illustrate the possible combinations but does not limit them:

[0103] A) Respiration inhibitors

[0104] - inhibitors of complex III at Qo site: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastro-bin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, pyribencarb, triclopyricarb / chlorodincarb, famoxadone, fenamidone, pyriminostrobin, bifujunzhi, metyltetraprole;

[0105] - inhibitors of complex III at Qi site: cyazofamid, amisulbrom, fenpicoxamid, florylpicoxamid, metarylpicoxamid;

[0106] - inhibitors of complex II: benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, pydiflumetofen, pyraziflumid, sedaxane, tecloftalam, thifluzamide, inpyrfluxam, pyrapropoyne, fluindapyr, isoflucypram, cyclobutrifluram;

[0107] - other respiration inhibitors: diflumetorim; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, meptyldinocap; ferimzone; organometal compounds: fentin salts, e.g. fentin-acetate, fentin chloride or fentin hydroxide; silthiofam;

[0108] - quinone outside inhibitor stigmatellin binding type: ametoctradin;

[0109] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0110] - C14 demethylase inhibitors: triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole , fluoxytioconazole, ipfentrifluconazole, mefentrifluconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines, piperazines: fenarimol, pyrifenox, triforine;

[0111] - Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;

[0112] - Inhibitors of 3-keto reductase: fenhexamid, fenpyrazamine;

[0113] - other Sterol biosynthesis inhibitors: chlorphenomizole;

[0114] C) Nucleic acid synthesis inhibitors

[0115] - RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M, ofurace, oxadixyl;

[0116] - other nucleic acid synthesis inhibitors: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, ipflufenoquin, quinofumelin;

[0117] D) Inhibitors of cell division and cytoskeleton

[0118] - tubulin polymerization inhibitors: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, pyridachlometyl;

[0119] - other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, phenamacril, fluopimomide;

[0120] E) Inhibitors of amino acid and protein synthesis

[0121] - methionine synthesis inhibitors: cyprodinil, mepanipyrim, pyrimethanil;

[0122] - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin;

[0123] F) Signal transduction inhibitors

[0124] - MAP I histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fludioxonil;

[0125] - mechanism unknown: quinoxyfen, proquinazid; G) Lipid and membrane synthesis inhibitors

[0126] - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;

[0127] - lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;

[0128] - compounds affecting cell membrane permeability and fatty acides: propamocarb;

[0129] - inhibitors of oxysterol binding protein: oxathiapiprolin, fluoxapiprolin;

[0130] H) Inhibitors with Multi Site Action

[0131] - inorganic active substances: Bordeaux mixture, copper, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

[0132] - thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;

[0133] - organochlorine compounds: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid;

[0134] - guanidines and others: guanidine, dodine, dodine free bas, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, fluoroimide, methasulfocarb, chinomethionat;

[0135] I) Cell wall synthesis inhibitors

[0136] - inhibitors of glucan synthesis: validamycin, polyoxin B;

[0137] - melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, tolprocarb;

[0138] - cellulose synthase inhibitors: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate;

[0139] J) Plant defence inducers

[0140] - acibenzolar-S-methyl, probenazol, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl- aluminum, phosphorous acid and its salts, calcium phosphonate, potassium phosphonate, potassium or sodium bicarbonate, dichlobentiazox;

[0141] K) Unknown mode of action

[0142] - bronopol, cyflufenamid, cymoxanil, dazomet, debacarb, diclocymet, diclomezine, difenzoquat, difenzoquat- methylsulfate, diphenylamin, fenitropan, fenpyrazamine, flumetover, flumetylsulforim, flusulfamide, flutianil, harpin, nitrapyrin, nitrothal-isopropyl, oxin-copper, seboctylamine, tebufloquin, tecloftalam, triazoxide, pyrisoxazole, , benziothiazolinone, bromothalonil, aminopyrifen, flufenoxadiazam;

[0143] L) Biopesticides

[0144] L1) Microbial pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleo-phila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructi-cola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paeni-bacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudo-zyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Tricho-derma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);

[0145] L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;

[0146] L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tene-brionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium sub-tsugae, Cydia pomonella granulovirus, Cryptophlebia leucotreta granulovirus, Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus, Helicoverpa zea nucleopolyhedrovirus, Helicoverpa zea single capsid nucleopolyhedrovirus, Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus, Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus;

[0147] L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and / or nematicidal activity: L- carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)- 7,11,13-hexadecatrienal, heptyl buty-rate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3, 13- octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z) 3,8, 11 -tetradecatrienyl acetate, (Z,E) 9,12- tetradecadien-1-yl acetate, (Z) 7 tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetra- decen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;

[0148] L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and / or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropic!, Sinorhizobium meliloti; 0) Insecticides from classes 0.1 to 0.29

[0149] 0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, pro-thiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;

[0150] 0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole;

[0151] 0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa- bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;

[0152] 0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;

[0153] 0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;

[0154] 0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;

[0155] 0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen; 0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;

[0156] 0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon;

[0157] 0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;

[0158] 0.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;

[0159] 0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;

[0160] 0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;

[0161] 0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;

[0162] 0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;

[0163] 0.16 Inhibitors of the chitin biosynthesis type 1 : buprofezin;

[0164] 0.17 Moulting disruptors: cyromazine;

[0165] 0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;

[0166] 0.19 Octopamin receptor agonists: amitraz;

[0167] 0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;

[0168] 0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;

[0169] 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone; 0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, spidoxamat;

[0170] 0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0171] 0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide;

[0172] 0.28 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlodiniliprole; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; cyhalodiamide;

[0173] 0.29 Chordotonal organ modulators: flonicamid;

[0174] 0.30 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocycloseram;

[0175] 0.33 Calcium-activated potassium channel modulators: acynonapyr;

[0176] 0.34 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin;

[0177] O.UN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropyl ate, chinomethionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, flu-ensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl but- oxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, actives on basis of Bacillus firmus (Votivo); fluazaindolizine; tyclopyrazoflor; sarolaner, lotilaner; benzpyrimoxan; tigolaner; oxazosulfyl; cyproflanilide, nicofluprole; indazapyroxamet; flupentiofenox; cyclobutrifluram.

[0178] P) Herbicides from the classes P1 to P15

[0179] P1) lipid biosynthesis inhibitors:

[0180] - ACC-herbicides: alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P- ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop- P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim;

[0181] - non ACC herbicides: benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;

[0182] P2) ALS inhibitors: - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron- sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron- ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;

[0183] - imidazolinones: imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr;

[0184] - triazolopyrimidine herbicides and sulfonanilides: cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam;

[0185] - pyrimidinylbenzoates: bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium;

[0186] - sulfonylaminocarbonyl-triazolinone herbicides: flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl;

[0187] - and triafamone;

[0188] P3) photosynthesis inhibitors: amicarbazone, inhibitors of the photosystem II, triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquat- dichloride and paraquat-dimetilsulfate;

[0189] P4) protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, epyrifenacil;

[0190] P5) bleacher herbicides: - PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, rimisoxafen;

[0191] - HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bipyrazone, fenpyrazone, cypyrafluone, tripyrasulfone, benquitrione, dioxopyritrione;

[0192] - bleacher, unknown target: aclonifen, amitrole flumeturon, bixlozone;

[0193] P6) EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);

[0194] P7) glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;

[0195] P8) DHP synthase inhibitors: asulam;

[0196] P9) mitosis inhibitors:

[0197] - group K1 : dinitroanilines: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin; phosphoramidates: amiprophos, amiprophos-methyl, and butamiphos; benzoic acid herbicides: chlorthal, chlorthal-dimethyl; pyridines: dithiopyr and thiazopyr; benzamides: propyzamide and tebutam;

[0198] - group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham;

[0199] P10) VLCFA inhibitors:

[0200] - chloroacetamides: acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor,

[0201] - oxyacetanilides: flufenacet and mefenacet;

[0202] - acetanilides: diphenamid, naproanilide, napropamide and napropamide-M;

[0203] - tetrazolinones: fentrazamide;

[0204] - other herbicides: anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, dimesulfazet and isoxazoline;

[0205] P11) cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam;

[0206] P12) decoupler herbicides: dinoseb, dinoterb and DNOC and its salts;

[0207] P13) auxinic herbicides:

[0208] 2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyralid-dimethylammonium, aminopyralid-tris(2- hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop- P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters; MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, florpyrauxifen -benzyl and 4-amino-3-chloro-5- fluoro-6-(7-fluoro-1 H-indol-6-y l)picolin io acid;

[0209] P14) auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;

[0210] P15) other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, tetflupyrolimet, tridiphane.

[0211] Q) Safeners

[0212] (quinolin-8-oxy)acetic acids, 1 -phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carboxylic acids, 1 -phenyl-4,5-dihydro-5-alkyl-1 H- pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha- oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4- (aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1 ,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.

[0213] Each of the one or more pesticides may be any substance, whether a chemical or biological agent, used to control pests, such as insecticides, herbicides, fungicides, acaricides, rodenticides, nematicides, and miticides.

[0214] Suitable insecticides may preferably be selected from the group consisting of neonicotinoids, bisamides, benzoylureas and carbamates.

[0215] It is especially preferred that each insecticide is selected from fenoxycarb, deltamethrin, piperonyl butoxide, imidacloprid, thiacloprid, acetamiprid, aldicarb, aldicarb sulfoxide, aldicarb sulfone, pirimicarb, chlorantraniliprole, terbufos, quinalphos, dyfonate, phosmet, carbaryl, etoxazole, thiamethoxam, flonicamid, etofenprox, phorate, profenofos, parathion, methylparathion, acephate, disulfoton, fenthion, fenvalerate, fipronil, baygon, methomyl, metaflumizone, pymetrozine, oxamyl, tau-fluvalinate, cypermethrin, cyfluthrin, bifenthrin, tetramethrin, prallethrin (mix of isomers), permethrin (mix of isomers), resmethrin (mix of isomers), pyrethrin (mix of isomers), spinetoram(J), abamectin (mix of isomers), fenobucarb (BPMC), methiocarb, isoprocarb (MIPC), spiro tetr am at, Spinosad, trichlorfon, fenamiphos sulfoxide, fenamiphos sulfone, 3-hydroxy carbofuran, aldrin, DDE (p-p1), DDD (o-p), DDD (p-p1), DDE (o- p), DDT (o-p1), dieldrin, endrin, endrin aldehyde, endrin ketone, isodrin, chlordecone, or mirex(Dodecachlorooctahydro- 1 H-1 ,3,4-(epimethanetriyl)cyclobuta[cd]pentalene).

[0216] Suitable herbicides may preferably be selected from the group consisting of triazines and other photosystem 2 inhibitors, 2,6-dinitroanilines, ACCase inhibitors, PPO inhibitors, synthetic auxins, sulfonyl ureas, bipyrillium herbicides, chloroacetanilides, triazolopyrimidines, pyrazoles and herbicidal safeners.

[0217] It is especially preferred that each herbicide is selected from paclobutrazol, diuron, linuron, isoproturon, alachlor, pendimethalin, chlorpropham, fenoprop, bentazone, metolachlor, propazine, bromacil, 2,4-DB, fenoxaprop, fluometuron, pinoxaden, molinate, cyanazine, simazine, atrazine, atrazine desethyl, or metribuzin.

[0218] Suitable fungicides may preferably be selected from the group consisting of pyrimidines, anilinopyrimidines, triazoles and other sterol demethylation inhibitors, triazolopyrimidines, MAP kinase inhibitors, strobilurins, adenosine deaminase inhibitors, pyrazoles and carboxamides.

[0219] It is especially preferred that each fungicide is selected from bitertanol, boscalid, bromuconazole, cyproconazole, diclobutrazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole,2-aminobutane, 8-hydroxyquinoline sulphate, 2-phenylphenol (OPP), aldi-morph, ampropylfos, anilazine, azoxystrobin, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, blasticidin-S, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cyazofamid, cymoxanil, cyprodinil, cyprofuram, dichlorophen, diclocymet, diclofluanid, diclomezin, dicloran, diethofencarb, diflumetorim, dimethirimol, dimethomorph, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, enestroburin, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluoromide, fluoxastrobin, flusulfamide, flutolanil, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, imazalil, iminoctadine, iprobenfos (IBP), iprodione, iprovalicarb, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copperoxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, kresoxim-methyl, mepronil, metalaxyl, methasulfocarb, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, pencycuron, phosdiphen, picoxystrobin, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene (PCNB), silthiofam, spiroxamine, sulphur and sulphur preparations, tecloftalam, tecnazene, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triazoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, validamycin, vinclozolin, zineb, ziram, or zoxamide. Suitable acaricides may preferably be selected from tebufenpyrad, aldicard, azinphosmethyl, carbophenothion, dimethoate, dicrotophos, triazophos, malathion, phosalone, methidathion, hexythiazox, propargite, spirodiclofen, methamidophos, monocrotophos, phenthoate, pirimiphosmethyl, epn, dichlorvos, ethion, fenitrothion, diazinon, chlorpyriphos, oxydemeton methyl, pyridaben, fenpropathrin, bifenazate, spiromesifen, fenpyroximate (mix of isomers), acequinocyl, or carbofuran.

[0220] It is particularly preferred that least one of the one or more pesticides is selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, diefenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacetate, epoxiconazole, fluxopyroxad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin and pendimethalin.

[0221] In the context of the agrochemical formulations, it is also well known that more than one pesticide may be used, resulting in a so-called combination formulation. Such combination formulations may have improved effects since the individual pesticides act in a synergistic manner or alternatively, the multiple pesticides may be active against different pests, for example, one pesticide may be a herbicide and another may be an insecticide.

[0222] Thus, in one embodiment, the agrochemical formulation comprises two or more pesticides.

[0223] Many such combination formulations are commercially available and are well known in the field. As such, the choice of which combination of pesticides is selected is not particularly limited.

[0224] In a preferred embodiment, at least one, more preferably at least two, of the two or more pesticides is / are selected from the group consisting of azoxystrobin, prothioconazole, pyraclostrobin, oxyfluorfen, diefenoconazole, trifloxystrobin, propiconazole, cyproconazole, flufenacetate, epoxiconazole, fluxopyroxad, fenbuconazole, tebuconazole, metaflumizone, pinoxaden, deltamethrin and pendimethalin.

[0225] In an embodiment, the agrochemical formulation additionally comprises one or more auxiliary selected from surfactants; dispersants; emulsifiers; wetters; further adjuvants; solubilizers; penetration enhancers; protective colloids; adhesion agents; rheology modifiers, preferably thickeners; repellents; compatibilizers; bactericides; anti-freezing agents; anti-foaming agents; colorants; tackifiers; binders; fillers; and preservatives.

[0226] The one or more auxiliary are distributed in the oil-phase component and the water-phase component, depending on the relative solubility of the one or more auxiliary. Suitably, the non-ionic surfactants, if present, are mainly present in the oil-phase component. Suitably, the anti-freezing agents and anti-foaming agents, if present, are mainly present in the water-phase component.

[0227] Suitable further adjuvants are compounds which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the pesticide on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

[0228] Suitable rheology modifiers include thickeners such as polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

[0229] Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

[0230] Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

[0231] Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

[0232] Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

[0233] Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0234] In certain embodiments, the oil-in-water emulsion-based agrochemical formulation may additionally comprise a surfactant (or emulsifier). The surfactant may be selected from any conventional emulsifiers typically used in the field of agrochemical compositions and formulations.

[0235] For example, the one or more surfactant may be selected from:

[0236] - products of the addition of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear Cs-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group;

[0237] - C12-18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol;

[0238] - glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof

[0239] - addition products of 15 to 60 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0240] - polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate;

[0241] - addition products of 2 to 15 mol ethylene oxide onto castor oil and / or hydrogenated castor oil;

[0242] - partial esters based on linear, branched, unsaturated or saturated C6-22 fatty acids, ricinoleic acid and 12- hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, - dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose); - mono-, di and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and salts thereof;

[0243] - wool wax alcohols;

[0244] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;

[0245] - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of Ce-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol, and

[0246] - polyalkylene glycols

[0247] Suitable non-ionic emulsifiers may be selected from the group consisting of copolymers containing ethylene oxide and propylene oxide monomers, alcohol alkoxylates, alkyl polyglucosides, aminopolyols, polyalkylene glycols, alkoxylated animal or vegetable fats and oils such as corn oil ethoxylates, soybean oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerol esters such as glycerol monostearate, fatty alcohol alkoxylates and oxoalcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylates, alkylphenol alkoxylates such as isononylphenol ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactants such as sorbitan fatty acid esters (e.g. sorbitan monooleate, and sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N- alkylgluconamides, alkylmethyl sulfoxides, alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide, or combinations thereof.

[0248] It is preferred that at least one of the one or more emulsifiers is a castor oil ethoxylate. Alternatively, it is preferred that at least one of the one or more emulsifiers is a copolymer containing ethylene oxide and propylene oxide monomers.

[0249] In one particular embodiment, at least one of the one or more emulsifiers is a castor oil ethoxylate and at least one of the one or more emulsifiers is a copolymer containing ethylene oxide and propylene oxide monomers.

[0250] Preferably, the agrochemical formulation comprises, relative to the total weight of the agrochemical formulation, a) from 0.1 to 20% w / w, more preferably from 0.2% to 10% w / w, most preferably from 0.25 to 5% w / w of the pickering emulsifier, calculated as the solids content of the aqueous polymer dispersion, b) from 0.1 to 80% w / w, more preferably from 1.0% to 70% w / w, most preferably from 5 to 50% w / w of the water- immiscible solvent or solvent mixture, c) from 0.01 to 80% w / w, more preferably from 0.1 to 70% w / w, most preferably from 0.5 to 50% w / w of the one or more agrochemical active ingredient(s), d) optionally, from 0.1 to 50% w / w, more preferably from 0.2% to 35% w / w, most preferably from 0.25 to 25% w / w of the one or more auxiliary, water up to 100 % w / w. Emulsion-in-water (EW) formulation

[0251] In an embodiment, the agrochemical formulation is an aqueous emulsion concentrate (EC). The emulsifiable concentrate (EC) is preferably stable in liquid form at 21 °C for at least 2 weeks. The emulsifiable concentrate (EC) is preferably stable in liquid form at -5 °C for at least 24 hours.

[0252] An emulsion-in-water (EW) formulation may be obtained by diluting the concentrate with water. It has been further found that the inventive emulsifiable concentrates (EC) form highly stable emulsions when mixed with water to form emulsions, so called emulsion-in-water (EW) formulations.

[0253] The stability of an emulsion-in-water formulation may be evaluated by determining how much sedimentation or cream is formed following homogenization (i.e. following emulsification). Both cream and sedimentation represent a departure from idealized emulsion behavior, where the disperse particles either rise to the surface (creaming) or sink to the bottom (sedimentation) depending on their density.

[0254] In order to quantify this beneficial feature of the emulsifiable concentrates (EC), a model emulsion system comprising 5.0 mL of the emulsifiable concentrate (EC) and 95.0 mL of water may be used, in which case a stable emulsion is defined as an emulsion that produces less than or equal to 1.5 mL of cream or sediment, 24 hours after formation of said emulsion.

[0255] As such, it is preferred that the emulsifiable concentrate (EC) forms a stable emulsion when 5.0 mL of said emulsifiable concentrate (EC) is combined with 95.0 mL of water and homogenized, wherein a stable emulsion is defined as an emulsion having less than or equal to 1 .5 mL of cream or sediment, 24 hours after formation of said emulsion.

[0256] More preferably the emulsion forms less than or equal to 1 .0 mL of cream or sediment, 24 hours after formation of said emulsion. Most preferably the emulsion forms less than or equal to 0.5 mL of cream or sediment, 24 hours after formation of said emulsion.

[0257] If the emulsion does produce a measurable level of sediment or cream, it is further preferred that the emulsion may be re-homogenized, i.e. re-emulsified, to reform a stable emulsion, wherein a stable emulsion is as defined as above, wherein less than or equal to 1.5 mL of cream or sediment is formed 30 minutes after re-homogenization, more preferably wherein less than or equal to 1.0 mL of cream or sediment is formed 30 minutes after re-homogenization, most preferably wherein less than or equal to 0.5 mL of cream or sediment is formed 30 minutes after rehomogenization.

[0258] Methods for the initial homogenization and re-homogenization are well known in the art, and the precise method used in such a test is not critical. That said, it is preferred that the homogenization is carried out by gentle inversion of the emulsion 10 times and that the re-homogenization is likewise carried out by gentle inversion of the emulsion 10 times.

[0259] As would be understood by the person skilled in the art, the threshold of how much cream or sediment would indicate that an emulsion would not be stable is dependent on the amounts of each phase present in the emulsion. As such, alternative tests, such as may be envisaged.

[0260] Use

[0261] The invention further relates to the use of an aqueous polymer dispersion as defined above as a pickering emulsifier in an oil-in-water emulsion.

[0262] The invention is illustrated by the following examples.

[0263] Examples

[0264] A. Materials and Methods

[0265] Transmittance of 532nm-Wavelength-Light

[0266] "Transmittance of 532nm-wavelength-light” means the transmittance measured with a wave length of 532 nm light using standard machines, such as preferably Hach Lange DR6000 spectrometer, compared to the transmittance of the standard, which usually is plain water suitable for such measurement, preferably being distilled or even bi-distilled water, at a concentration of 0.01 wt.% and a cuvette of 1 centimeter length of dispersion for the rays to pass through.

[0267] Water Solubility of Solvents

[0268] The water solubility of the solvent was determined according to a method based on CIPAC MT157.1 and OECD 105 via the assessment of undissolved solvent in water after vigorous mixing and standing. Herein, various amounts of solvent and water were mixed with vigorous shaking in a glass-stoppered graduated cylinder or separating funnel, followed by standing for at least 30 min to enable separation. For example, if undissolved solvent was observed after thorough mixing of 0.1 g solvent in 100 mL of water, the solvent had a water-solubility equal to or below 0.1 % (< 1 g / L). This method can be repeated with various amounts of solvent and water to enable the determination of the watersolubility of the solvent. CIPAC D Water

[0269] CIPAC D water was provided according to a standard recipe published by CIPAC "MT 18.1.4”: Standard Waters .The water had a hardness of 342 ppm, with a 4: 1 mixture of Ca:Mg ions at pH 6 to 7.

[0270] Pickering Emulsifier Test Methods

[0271] 1. Pickering Oil-In-Water Emulsion (EW) Formulation Generation

[0272] The "oil phase” was generated by mixing the solvent(s), active ingredient(s), and additionally surfactant(s) (e.g., adjuvant) under stirring until fully dissolved. The "water phase” was generated by mixing the polymer (pickering emulsifier), defoamer and anti-freeze under stirring until fully dissolved. The "water phase” was added to the "oil phase” and emulsified using an Ultra Turrax for 2 minutes operating at 12000 rpm to form a stable, free-flowing pickering oil- in-water emulsion (EW).

[0273] 2. Pickering Emulsion (EW) Formulation Stability at Room Temperature (21 °C)

[0274] If the resulting EW remained stable without any precipitation for at least 24 hours upon storage at room temperature (21 °C), then this was termed "stable”. S = stable, L = liquid, U1 = unstable due to separation U2 = unstable due to solidification.

[0275] 3. Pickering Emulsion Stability Upon Dilution to 5% at Room Temperature (21 °C)

[0276] The pickering emulsion (EW) was tested for its dispersibility by the effect known as blooming and stability upon dilution in water.

[0277] The emulsions were assessed according to their spontaneous emulsification when the concentrate is added to water (known in the art as "blooming") with a visual assessment given on a scale of 1 to 5, whereby 1). Excellent, "cloud of emulsion”, does not sink to bottom of cylinder. 2). Good, "cloud of emulsion”, but sinks to bottom of cylinder 3). Okay, "poor emulsion cloud”, larger droplets 4). Poor, "no emulsion cloud”, small "particles” observed 5). Very poor, no emulsion, oil and water phases immediately separate".

[0278] Emulsions (EW) were prepared in the following examples and the resulting 5% w / w emulsions in various water hardness at 21 °C after 24 hours were assessed. Emulsion stability was determined as a function of time, with the amount of either cream or sediment measured.

[0279] To measure emulsion stability, 5.0 mL of the pickering emulsion (EW) was diluted in 95.0 mL CIPAC D water in a 100 mL measuring cylinder. The resulting emulsion stability was assessed after 1 , 2, 4 and 24 hours. A highly stable emulsion does not form cream or sediment, or has less than 2.0 mL cream or sediment after 24 hours, and can be readily re-emulsified after 24 h of standing without the formation of cream or sediment, with such re-emulsified emulsions assessed 30 minutes after re-emulsification. Both the initial emulsification and the re-emulsification were achieved by gently inverting the emulsion 10 times. In the following tables Y (i.e. yes) indicates that at most 2.0 mL cream or sediment is observed after 24 hours, whilst N (i.e. no) indicates that more than 2.0 mL cream or sediment is observed after 24 hours.

[0280] B. Aqueous Polymer Dispersions

[0281] Aqueous polymer dispersions 1 , 2 and 3 were prepared as follows. The individual amounts of the components are indicated in the tables below.

[0282] A 4 L glass reactor (temperature control, anchor stirrer and reflux condenser under nitrogen gas atmosphere) was precharged with a solution of sodium acetate, carboxymethyl cellulose (Finnfix 10, CP Kelco) and 95 wt.-% maltodextrin with a dextrose equivalent of 10 (CDry MD01910, Cargill) in demineralized water. The mixture was heated to 70 °C while stirring at 120 rpm to obtain a transparent solution.

[0283] In a second glass reactor, an emulsion was prepared. Emulsifiers in accordance with the tables below, such as lauryl ether sulfate (Disponil FES 27, BASF), alkyldiphenyloxide disulfonate (Dowfax 2A1 , Dow) or sodium octyl succinic acid (Lumiten I - SC, BASF), were dissolved in water and a mixture of vinyl acetate, vinyl laurate and methacrylic acid ester- PEG C18 (Visiomer C18 PEG 1105, Evonik) were added dropwise. A stable emulsion was obtained (Feed 1). Optionally, 2-ethylhexyl-thioglycolate was added.

[0284] As a first initiator redox system, separate solutions of 7 wt.-% of sodium persulfate in water or 10.0 wt.-% tert-butyl hydroperoxide solution in water (Feed 2) and 2 wt.-% of ascorbic acid (Lutavit C) in water or a 2.5 wt.-% acetone bisulfite solution (Feed 3) were provided. The 2.5 wt.-% acetone bisulfite solution was obtained as discussed for Feed 5 below. To initiate the reaction, 5 wt.-% of the total amount of Feed 1 was added to the precharge at 70 °C and stirred for 5 min. Feed 2 and Feed 3 were dosed in simultaneously. The total dosing time of Feed 2 and Feed 3 was 255 min. 15 min after starting the dosing in of Feed 2 and 3, the remaining Feed 1 was dosed in over a period of 210 min.

[0285] A second redox initiator system was used to reduce the residual monomer content. For this second redox initiator system, a 10.0 wt.-% tert-butyl hydroperoxide solution in water (Feed 4) and a 2.5 wt.-% acetone bisulfite solution (Feed 5) were provided. Feed 5 was obtained as follows: 7.62 g sodium disulfite (Na2S2O5) were dissolved in 87.6 g deionized water (Mixture A). 95.22 g aqueous NaHSOa (8.8 wt.-%) and 4.78 g acetone were mixed (Mixture B). Mixtures A and B were mixed to obtain 100.00 g acetone bisulfite solution (13.1 wt.-%), which was diluted with water to obtain a 2.5 wt.-% acetone bisulfite solution (Feed 5). After Feeds 1, 2 and 3 were dosed in, the tert-butyl hydroperoxide solution (Feed 4) was added. Subsequently, the acetone bisulfite solution (Feed 5) was dosed in over the course of 30 min. Then, a small amount of a 15 wt.-% of hydrogen peroxide solution in water (Feed 6) was added to achieve a white color lasting dispersion. The residual monomer content of vinyl acetate was found to be less than 300 ppm. The acetaldehyde content was less than 800 ppm. Residual monomer contents were measured by gas chromatography against calibrated standards.

[0286] After cooling to 25 °C, the dispersion was filtered with a nylon filter (125 pm).

[0287] Table: Feed Compositions of Aqueous Polymer Dispersions 1 , 2 and 3

[0288] The table below shows the concentrations of the components of aqueous polymer dispersions 1 , 2 and 3 in parts per hundred million (pphm), as well as the characteristics of aqueous polymer dispersions 1 , 2 and 3. The aqueous polymer dispersions were characterized by total solids content, transmittance of 532-nm wavelength-light (determined according to the method above), pH value (determined at room temperature, i.e. 23 °C, and atmospheric pressure), the amount of coagulum remaining in the filter (determined by washing the filter with water and comparing the weight before and after filtration), and the particle size distribution D50 (determined in accordance with ISO 13320:2009).

[0289] Table: Composition (Solids Content) and Characteristics of Aqueous Polymer Dispersions 1 and 2 n.d. = not determined C. Pickering Emulsion (EW) Tests

[0290] In accordance with the methods described above and the table below, pickering oil-in-water emulsion (EW) formulations were provided and evaluated. As Surfactant 1, ethoxylated castor oil (54 mol% ethoxylated) was used.

Claims

Claims1 . An oil-in-water emulsion-based agrochemical formulation comprising:I) an oil-phase component comprising one or more agrochemical active ingredient(s) dissolved in a water-immiscible solvent or solvent mixture, andII) a water-phase component, ill) a pickering emulsifier, obtainable by radical aqueous emulsion polymerization of a mixture comprising a) ethylenically unsaturated monomers M, with M comprising(1) at least one vinyl ester M1, preferably comprising vinyl acetate, more preferably comprising vinyl acetate at least 50%, and(2) at least one (meth)acrylic acid ester M2 optionally comprising methacrylic acid as minor component, the (meth)acrylic acid in the methacrylic acid ester being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 2 to 40 alkylene oxide AO-units, most preferably 25 AO-units, with the PAO preferably being further linked via an ether-function to an C1 to 024, preferably at least 04, more preferably at least 06, even more preferably 08 to 024-aliphatic alkanol, most preferably a 018-aliphatic alkanol, with the AO being preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50, more preferably at least 75, even more preferably at least 90 wt.% most preferably essentially only EO, based on total AO; preferably comprising methacrylic acid, more preferably with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%;(3) optionally further monomers M3 polymerizable with M1 and M2, preferably none; b) 1 to 15, preferably 2 to 10%, based on the total weight of monomers M, of a carboxyl- groups-containing compound CGCC being selected from a compound bearing in its structure at least three carboxyl-groups of which at least 10 and at most 90 percent are being deprotonated, selected from the group comprising citric acid, isocitric acid; ethylendiamintetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acid; oligomeric and poly methacrylic acid; trimelitic acid; oligomeric aminoacids with carboxy groups such as polyaspartic acid; oligomeric and polyglutaminic acid; oligomeric and polyacetates with carboxygroups such as poly (glyoxalic)aldehyde; carboxylated oligomeric and polymeric saccharides such as oxidized starch (mixtures of amylopektines, amylose); polyglucuronates; cellulose oxidized to cellouronate; natural polycarboxylatic polysaccharide such as xylanes; pektines acid; alginic acid; carboxymethylated polysaccharides based on1 ,4-polyglucanes, 1 ,3-polyglucanes, 1,6-polyglucanes; Poly-uronic acids based on 1,4- polyglucanes, 1 ,3-polyglucanes, 1,6-polyglucanes; polygalacturonic; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC”);c) at least one non-carboxylated saccharide and / or polysaccharide S, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35wt% based on the total weight of monomers M; d) at least one emulsifier selected from non-ionic and anionic surfactants; e) optionally sulfate ions; and f) optionally sulfite ions; wherein - preferably - the amount of M1 is from 80 to 99,99 mol%, and the amount of M2 is from 0,01 to 20 mole%, and preferably at most 10, even more preferably at most 5, more preferably at most 2%, the total amount of M1 plus M2 being 100 weight percent, and wherein the dispersion has - after the end of the polymerization - a pH of up to 4.

2. The agrochemical formulation according to claim 1, wherein the vinyl ester M1 monomer comprises vinyl acetate with at least 50%, even more preferably at least 90% based on the total molar amount of vinyl esters, and the least one (meth)acrylic acid ester M2 is a (meth)acrylic acid being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 20 to 30 alkylene oxide AO-unit, most preferably 25 AO-units, with the PAO preferably being further linked via an ether- function to an C14 to C22 -aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, with the AO being selected from EO and PO and / or BuO, more preferably EO and PO, with the EO in an amount of from 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on total AO; further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%; and M3 being not comprised.

3. The agrochemical formulation according to claim 2, wherein the vinyl ester M1 monomer comprises vinyl acetate with at least 90% based on the total molar amount of vinyl esters, preferably essentially only vinyl acetate, and the least one (meth)acrylic acid ester M2 is a (meth)acrylic acid being bonded via an ether-function to a polyalkylene oxide-derived-block PAO, wherein the PAO consists of 23 to 27 alkylene oxide AO, most preferably on average 25 AO-units, with the PAO preferably being further linked via an ether-function to essentially C16 / 18-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, with the AO being essentially only EO; further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of from about 70 w% / 30w% to 80 w% / 20w%, more preferably about 75 w% / 25w%.

4. The agrochemical formulation according to claim 3, wherein M1 is vinyl acetate, andthe least one (meth)acrylic acid ester M2 is a methacrylic acid being bonded via an ether-function to a polyethylene oxide block PEO, wherein the PEO consists of on average 25 AO-units, with the PEO being further linked via an ether-function to a C16 / 18-aliphatic alkanol, further comprising methacrylic acid, with the methacrylic acid ester and the free methacrylic acid being in a ratio of about 75 w% / 25w%.

5. The agrochemical formulation according to any of the preceding claims, wherein the CGCC is a carboxyl-groups-containing compound being selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose, preferably in amounts of 2.5 to 10 most preferably about 5 weight percent based on the total amount of monomers M1+M2+M3.

6. The agrochemical formulation according to any of the preceding claims, wherein the dispersed polymer particles have a D[4,3] value as determined by static light scattering of at least 100 and up to 1000 nm.

7. The agrochemical formulation according to any of the preceding claims , wherein at least one saccharide and / or polysaccharide S is a starch degradation product, preferably a maltodextrin, in an amount of 10 to 30, preferably 15 to 25 wt%, more preferably 17 to 23 wt%, based on the total weight of monomers M.

8. The agrochemical formulation according to claim 7, wherein S is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range from 2 to 40%.

9. The agrochemical formulation according to any of the preceding claims, wherein as compound S a degraded starch is employed having a number average molecular weight in the range from 300 to 2000 Dalton, as determined by osmometry, and preferably in a range of from 5 to 150, more preferably up to 70, even more preferably up to 50, and more preferably from 10, even more preferably from 15, and most preferably from 20, each in weight percent based on the total weight of monomers M1+M2+M3.

10. The agrochemical formulation according to any of the preceding claims, wherein the agrochemical active ingredient is a pesticide, preferably selected from an insecticide, a herbicide, a fungicide, and combinations thereof.11 . The agrochemical formulation according to any of the preceding claims, wherein the water- immiscible solvent comprises at least one solvent having a water solubility of less than or equal to 1.5% w / w.

12. The agrochemical formulation according to claim 11, wherein the water-immiscible solvent is selected from hydrocarbons, vegetable oils, amide solvents, ester solvents, carbamate-based solvents, and mixtures thereof.

13. The agrochemical formulation according to any of the preceding claims, additionally comprising one or more auxiliary selected from surfactants; dispersants; emulsifiers; wetters; further adjuvants; solubilizers; penetration enhancers; protective colloids; adhesion agents; rheology modifiers, preferably thickeners; repellents; compatibilizers; bactericides; anti-freezing agents; anti-foaming agents; colorants; tackifiers; binders; fillers; and preservatives.

14. The agrochemical formulation according to any of the preceding claims, comprising, relative to the total weight of the agrochemical formulation, a) from 0.1 to 20% w / w, more preferably from 0.2% to 10% w / w, most preferably from 0.25 to 5% w / w of the pickering emulsifier, b) from 0.1 to 80% w / w, more preferably from 1 .0% to 70% w / w, most preferably from 5 to 50% w / w of the water-immiscible solvent or solvent mixture, c) from 0.01 to 80% w / w, more preferably from 0.1 to 70% w / w, most preferably from 0.5 to 50% w / w of the one or more agrochemical active ingredient(s), d) optionally, from 0.1 to 50% w / w, more preferably from 0.2% to 35% w / w, most preferably from 0.25 to 25% w / w of the one or more auxiliary, e) water up to 100 % w / w.

15. The agrochemical formulation according to any of the preceding claims, which is an aqueous emulsion concentrate.

16. The use of an aqueous polymer dispersion obtainable by radical aqueous emulsion polymerization as defined in any one of claims 1 to 9 as a pickering emulsifier in an oil-in-water emulsion.

Images