WO2017084946A1

WO2017084946A1 - High-payload granules containing a sulfosuccinate surfactant and a polycarboxylic acid

Info

Publication number: WO2017084946A1
Application number: PCT/EP2016/077166
Authority: WO
Inventors: Shingo Fujii
Original assignee: Basf Se
Priority date: 2015-11-18
Filing date: 2016-11-09
Publication date: 2017-05-26
Also published as: CN108347921A; JP2018534308A; KR20180083386A; JP6902540B2

Abstract

The instant invention relates to a process for manufacturing pesticide granules, comprising the steps of preparing a premix comprising a mixture of bentonite and silicates, a mixture of a sulfosuccinate surfactant and a polycarboxylic acid, and a pesticidal composition comprising a pesticide and a liquid, and subsequently extruding the premix, wherein the weight ratio of bentonite to silicates is from 10:1 to 1:10. The invention also relates to pesticide granules comprising a mixture of bentonite and silicates, a mixture of sulfosuccinate surfactant and a polycarboxylic acid, and a pesticide, wherein the weight ratio of bentonite to silicates is from 10:1 to 1:10.

Description

High-payload granules containing a sulfosuccinate surfactant and a polycarboxylic acid

Description The instant invention relates to a process for manufacturing pesticide granules, comprising the steps of 1 ) preparing a premix comprising a solid carrier selected from inorganic, and organic inert materials; a mixture of a sulfosuccinate surfactant, and a polycarboxylic acid; and a pesticidal composition comprising a pesticide and a liquid; and 2) subsequently extruding the mixture. The invention also relates to pesticide granules obtained from said process for manufacturing; and to pesticide granules comprising a solid carrier selected from inorganic, and organic inert materials; a mixture of sulfosuccinate surfactant, and a polycarboxylic acid; and a pesticide. Furthermore, the invention relates to a method of controlling undesired insect or mite attack, harmful fungi, and/or undesired vegetation, and/or for regulating the growth of plants, wherein the pesticide granules, or pesticide granules obtainable by the process for manufacturing pesticide granules, are allowed to act on the respective pests, their environment, or the crop plants to be protected from the respective pest, on the soil, and/or on the crop plants, and/or on their environment. The invention comprises combinations of embodiments with other embodiments, independent of their respective degree of preference.

Pesticide granules are a convenient type of formulation in agrochemical industry. They are usually produced by extrusion. Extrusion, however, requires a defined range of viscosity of the premix to be extruded. In case the premix is too fluid, the extrusion yield decreases dramatically. However, many pesticides are only available as liquid compositions. Either these pesticides are already formulated as commercial compositions for end-customer use, or they are produced in a liquid - such as polymorphs. In case such liquid compositions are to be used in the premix, they can only be admixed in low amounts in order to maintain a minimum viscosity of the premix. In turn, this translates into low concentrations of the pesticides in the produced granules.

It was an object of the invention to supply a process for manufacturing pesticidal granules, wherein higher amounts of pesticidal compositions comprising a liquid can be incorporated.

This object was solved by the process for manufacturing pesticide granules of claim 1.

Usually, the extrudate is granulated in a subsequent step 3). The granules are typically water-dis- persible granules. Emulsifiable granules are usually excluded. The extrudate may also be processed to powders, or pastes.

The process may also comprise a preceeding step 0, wherein a pesticidal composition comprising the pesticide and the liquid is provided. Usually, the pesticide is dissolved or dispersed in the liquid in step 0), preferably dissolved. The premix contains a solid carrier selected from inorganic, and organic inert materials. The term inert within the context of this invention may relate to compounds that do not have any pesticidal, or surface-active effects. The term solid usually refers to compounds, which are solid at a temperature below 40 °C, preferably below 80 °C, most preferably below 150 °C. Typical inorganic inert materials are mineral earths, such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide. Typical organic inert materials are polysaccharides, such as cellulose, cereal or starch, and materials of animal origin, such as cereal meal, tree bark meal, wood meal, and nut- shell meal. Mixtures of solid carriers may also be used.

Usually, the term "silicates" relates to the pure condensation products of silicic acid, or their salts. Accordingly, the term silicates does not comprise materials with more than 5 wt%, preferably more than 1 wt% of other elements, or their oxides, e.g. oxides of alkaline metals, alkaline earth metals, or transition metals of period 4, such as Fe203, AI2O3, Na20, K2O, CaO, or MgO. Specifically, the term silicates does not comprise volcanic glassy powder, which is sometimes referred to sirasu. Typically, silicates are in the form of powders. Accordingly, the silicates do usually not form hollow

structures, such as hollow spheres.

In one embodiment, the solid carrier is an inorganic inert material. In another embodiment, the solid carrier is an organic inert material. In yet another embodiment, the solid carrier is a silicate. In yet another embodiment, the solid carrier is a bentonite. In yet another embodiment, the solid carrier is calcium sulfate In yet another embodiment, the solid carrier is diatomaceous earth. In yet another embodiment, the solid carrier is a mixture of bentonite, and silicates, preferably amorphous silicates. The solid carrier is usually water-insoluble. The solid carrier may have a water-solubility at 25 °C of up to 1 g/l, preferably up to 0.1 g/l, and most preferably up to 0.01 g/l.

The amount of solid carrier in the premix can be from 1 to 90 wt% based on the total weight of the premix, preferably from 5 to 80 wt%, more preferably from 20 to 60 wt%, based on the total weight of the premix. The amount of solid carrier in the premix can be up to 99 wt%, preferably up to 75 wt%, more preferably up to 65 wt%, based on the total weight of the premix. The amount of solid carrier in the premix is usually at least 10 wt%, preferably at least 25 wt%, and most preferably at least 35 wt%, based on the total weight of the premix.

The amount of solid carrier in the pesticide granules can be from 1 to 99 wt% based on the total weight of the premix, preferably from 5 to 80 wt%, more preferably from 20 to 75 wt%, most prefera- bly from 50 to 65 wt%, based on the total weight of the premix. The amount of solid carrier in the premix can be up to 90 wt%, preferably up to 85 wt%, more preferably up to 75 wt%, based on the total weight of the premix. The amount of solid carrier in the premix is usually at least 10 wt%, preferably at least 45 wt%, and most preferably at least 55 wt%, based on the total weight of the premix. In one embodiment, a mixture of bentonite and silicates is used for preparing the premix. The weight ratio of bentonite to silicates in the premix, and in the pesticide granules, is usually in the range from 10: 1 to 1 : 10, preferably from 5: 1 to 1 :5, most preferably from 5: 1 to 1 :2.

The amount of bentonite in the premix is usually from 10 to 80 wt%, preferably from 20 to 70 wt%, more preferably from 20 to 40 wt%, most preferably from 20 to 35 wt%, based on the total weight of the premix. Usually, the amount of bentonite in the premix is less than 40 wt%, preferably less than 35 wt%, based on the total weight of the premix.

The amount of silicates in the premix is usually from 1 to 50 wt%, preferably from 10 to 30 wt%, and most preferably from 10 to 25 wt%, based on the total weight of the premix. The amount of silicates in the premix is usually at least 8 wt%, preferably at least 10 wt %, based on the total weight of the premix. The amount of silicates is usually up to 40 wt%, preferably up to 25 wt%, based on the total weight of the premix.

In one embodiment, the amount of bentonite in the premix is from 20 to 40 wt%, and the amount of silicates in the premix is from 10 to 30 wt%, based on the total weight of the premix. In another embodiment, the amount of bentonite in the premix is from 20 to 35 wt%, and the amount of silicates in the premix is from 10 to 25 wt%, based on the total weight of the premix.

The amount of bentonite in the pesticide granules is usually from 10 to 80 wt%, preferably from 20 to 70 wt%, more preferably from 20 to 50 wt% based on the total weight of the pesticide granules. Usually, the amount of bentonite in the pesticide granules is less than 55 wt%, preferably less than 50 wt%, based on the total weight of the pesticide granules.

The amount of silicates in the pesticide granules is usually from 1 to 50 wt%, preferably from 10 to 50 wt%, most preferably from 10 to 35 wt%, and in particular from 15 to 35 wt% based on the total weight of the premix. The amount of silicates in the premix is usually at least 10 wt%, preferably at least 12 wt %, based on the total weight of the premix. The amount of silicates is usually up to 40 wt%, preferably up to 35 wt%, based on the total weight of the premix.

In one embodiment, the amount of bentonite in the pesticide granules is from 20 to 70 wt%, and the amount of silicates in the pesticide granules is from 10 to 50 wt%, based on the total weight of the pesticide granules. In another embodiment, the amount of bentonite in the pesticide granules is from 20 to 50 wt%, and the amount of silicates in the pesticide granules is from 10 to 35 wt%, based on the total weight of the pesticide granules. In yet another embodiment, the amount of bentonite in the pesticide granules is from 20 to 50 wt%, and the amount of silicates in the pesticide granules is from 15 to 35 wt%, based on the total weight of the pesticide granules.

The premix comprises a mixture of a sulfosuccinate surfactant, and a polycarboxylic acid.

The sulfosuccinate surfactant relates usually to derivatives of sulfonated succinate with an HLB value from 25 to 40, preferably from 30 to 35. The HLB value for ionic substances, such as sulfosuc- cinates, is usually measured in comparison to other surfactants, such as described by Middleton J., A titration Method for the Determination of the HLB's of Emulsifiers, J. Soc. Cosmetic Chemists 1968, vol.19, p.129-136.

The concentration of the sulfosuccinate surfactant in the premix may be from 0.1 to 20 wt%, prefera- bly from 0.5 to 10 wt%, and most preferably from 1 to 10 wt%, based on the total weight of the premix. The concentration of the sulfosuccinate surfactant in the pesticide granules may be from 0.1 to 20 wt%, preferably from 0.5 to 10 wt%, most preferably from 1 to 10 wt%, and in particular from 2 to 6 wt%, based on the total weight of the pesticide granules. Usually, the sulfosuccinate surfactant is an ester of sulfosuccinate with a C1-C15 aliphatic, or a C6- C10 aromatic, or a C1-C15 mixed aliphatic and aromatic alcohol. In one embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with a C1-C15 aliphatic alcohol. In another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with a C1-C10 aliphatic alcohol. In another embodiment, the sulfosuccinate is an ester of sulfosuccinate with a C5-C10 aliphatic alcohol. In another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with a C6-C10 aromatic alcohol. In yet another embodiment, the sulfosuccinate surfactant is an ester with a C1-C15 mixed aliphatic and aromatic alcohol.

In one embodiment the C1-C15 aliphatic alcohol is branched. In another embodiment, the C1-C15 aliphatic alcohol is linear.

Examples of C1-C15 aliphatic alcohols are methanol, ethanol, 1-propanol, 2-propanol, n-butanol, iso- butanol, tert-butanol, n-pentanol, amyl alcohol, neopentyl alcohol, diethyl carbinol, 2-methyl butyl al- cohol, isopentanol, n-hexanol, 2-hexanol, 3-hexanol, 2-methylpentan-1-ol, 3-methyl-pentan-1-ol, 4- methylpentan-1-ol, 2-methylpentan-2-ol, 3-methylpentan-2-ol, 4-methylpentan-2-ol, 2-methylpentan- 3-ol, 3-methylpentan-3-ol, 2,2, dimethylbutan-1-ol, 2,3-dimethylbutan-1-ol, 3,3-dimethylbutan-1-ol, 2,3-dimethylbutan-2-ol, 3,3-dimethylbutan-2-ol, 2-ethylbutan-1-ol, n-heptanol, 2-heptanol, 3-hep- tanol, 4-heptanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-ethyl-1-pentanol, 3-ethyl-1-pentanol, n-octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-me- thyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-ethyl-hexan-1-ol, 3-ethyl-hexan-1-ol, 4- ethyl-hexan-1-ol, 2-octanol, 3-octanol, 4-octanol, n-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5- nonanol, 2-methyl-octan-1-ol, 3-methyl-octan-1-ol, 4-methyl-octan-1-ol, 5-methyl-octan-1-ol, 5-me- thyl-octan-1-ol, 6-methyl-octan-1-ol, 2-ethyl-heptan-1-ol, 3-ethyl-heptan-1-ol, 4-ethyl-heptan-1-ol, 5- ethyl-heptan-1-ol, triisopropyl methanol, n-decanol, 7-methyl-octan-1-ol, n-undecanol, n-dodecanol, n-tricecanol, isotridecyl alcohol, n-tetradecanol, n-pentadecanol. In one embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with an alcohol selected from hexanol, heptanol, oc- tanol, nonanol, decanol, and their isomers. In another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with an alcohol selected from octanol, and its isomers. In yet another em- bodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with an alcohol selected from branched octanols. In yet another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with n-octanol. In yet another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with an alcohol selected from n-octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4- methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-ethyl-hexan-1-ol, 3-ethyl-hexan-1-ol, 4-ethyl-hexan-1-ol, 2-octanol, 3-octanol, and 4-octanol. In yet another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with an alcohol selected from 2-ethyl-hexan-1-ol, 3-ethyl- hexan-1-ol, 4-ethyl-hexan-1-ol. In yet another embodiment, the sulfosuccinate surfactant is an ester of sulfosuccinate with 2-ethyl-hexan-1-ol. Examples of C6-C10 aromatic alcohols are phenol, and naphthyl alcohol. Examples of C1-C15 mixed aliphatic and aromatic alcohols are benzyl alcohol, 2-phenyl-ethan-1-ol, 3-phenyl-propan-1-ol, 4-phe- nyl-butan-1-ol, 5-phenyl-pentan-1-ol, 6-phenyl-hexan-1-ol, 7-phenyl-heptan-1-ol, 8-phenyl-octan-1- ol, 9-phenyl-nonan-1-ol, 2-methyl-phenol, 3-methyl-phenol, 4-methyl-phenol, 4-ethyl-phenol, 4-pro- pyl-phenol, 4-isopropyl-phenol, 4-butyl-phenol, 4-tert-butyl-phenol, 4-pentyl-phenol, 4-hexyl-phenol, and 1-(2-naphtyhl)ethanol.

The term ester of sulfosuccinate may relate to the monoester, or the diester of sulfosuccinate. Usually the term ester of sulfosuccinate relates to the diester of sulfosuccinate. The molecular weight of the sulfosuccinate surfactant is usually below 1000 g/mol, preferably below 500 g/mol.

Sulfosuccinate surfactants of the above types are commercially available.

The polycarboxylic acid may usually relate to polymers comprising monomers I comprising carbox- ylic acid groups in polymerized form. Usually the monomers with carboxylic acid groups are ethyleni- cally unsaturated. Typically monomers I are selected from C3-C8 ethylenically unsaturated monomers comprising carboxylic acid groups. Examples of monomers I are acrylic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, mesaconic acid, or itaconic acid in polymerized form. In one embodiment, monomer I is acrylic acid. In another embodiment, monomer I is itaconic acid. In yet another embodiment, the monomer I is maleic acid. In yet another embodiment, monomer I is crotonic acid.

The polycarboxylic acid is typically either a homopolymer, or a copolymer of a monomer I with a monomer II, and optionally further monomers. In one embodiment, the polycarboxylic acid is a copolymer comprising monomer I, and monomer II. In another embodiment, the polycarboxylic acid is a copolymer consisting of monomer I and monomer II. Usually, however, the polycarboxylic acid is not a poly (meth)acrylate. Typical monomers II are ethylenically unsaturated and comprise a C1-C20 aliphatic, aromatic, or mixed aliphatic and aromatic group. In one embodiment, monomers II are hydrocarbons, such as Ci- C2o alkyl-oolefins, C6-Ci2 aryl-oolefins, and mixed Ci-C2o alkyl-aryl-oolefins.

In one embodiment, the monomer II is a Ci-C2o alkyl-oolefins, such as Ci-C2o alkyl-oolefins.

In another embodiment, the alkyl-oolefin is a Ci-Cio alkyl-a-olefin. In another embodiment, the alkyl- oolefin is a C4-Cio alkyl-oolefins. In yet another embodiment, the alkyl-oolefin is a C6-Cio alkyl-o olefins.

Examples of Ci-C2o a-olefins are propene, 1-butene, isobutene, 1-pentene, 2-methylbut-1-ene, 3- methylbut-1-ene, 1-hexene, 2-methylpent-1-ene, 3-methylpent-1-ene, 4-methylpent-1-ene, 3-meth- ylenepentane, 3,3-dimethylbut-1-ene, 1-heptene, 2-methylhex-1-ene, 3-methylhex-1-ene, 4- methylhex-1-ene, 5-methylhex-1-ene, 2-ethylpent-1-ene, 3-ethylpent-1-ene, 2,4-dimethylpent-1-ene, 2,3-dimethylpent-1-ene, 2-methyl-3-methylenepentane, 1-octene, 2-methylhept-1-ene, 3-methylhept- 1-ene, 4-methylhept-1-ene, 5-methylhept-1-ene, 6-methylhept-1-ene, 2-ethylhex-1-ene, 3-ethylhex- 1-ene, 4-ethylhex-1-ene, 4-methyleneheptane, 2-methyl-3-methylene-hexane, 2,4-dimethyl-3-meth- ylene-pentane, 3-methyl-4-methylene-hexane, 3-ethyl-2-methylpent- 1-ene, 3-ethyl-4-methylpent-1- ene, 2,4,4-trimethylpent-1-ene, 3,4-dimethylhex-1-ene, 4,5-dimethylhex-1-ene, 2,5-dimethylhex-1- ene, 1-nonene, 2-methyl-non-1-ene, 3-methyl-non-1-ene, 4-methyl-non-1-ene, 5-methyl-non-1-ene, 6-methyl-non-1-ene, 7-methyl-non-1-ene, 8-methyl-non-1-ene, 7-methyl-oct- 1-ene, 6,6-dimethyl- hept-1-ene, 5,5,5-trimethyl-hex-1-ene, 2-ethyl-hept-1-ene, 3-ethyl-hept-1-ene, 4-ethyl-hept-1-ene, 5- ethyl-hept-1-ene, 1-decene, 2-methylnon-1-ene, 3-methylnon-1-ene, 4-methylnon-1-ene, 5-methyl- non-1-ene, 6-methylnon-1-ene, 7-methylnon-1-ene, 8-methylnon-1-ene, 7,7-dimethyloct-1-ene, 6,6,6-trimethylhept-1-ene, 2-ethyloct-1-ene, 3-ethyloct-1-ene, 4-ethyloct-1-ene, 5-ethyloct-1-ene, 6- ethyloct-1-ene, 1-undecene, 1-dodecene, 1-tridecene, and 12-methyledodec-1-ene. In one embodiment, the alkyl-oolefins are selected from branched C2-C20 alkyl-oolefins. In another embodiment, the alkyl-oolefins are selected from propene, isobutene, 3-methylbut-1-ene, 4-methylpent-1-ene, 3,3-dimethylbut-1-ene, 4,4-dimethylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trimethylhex-1-ene, 6,6-dimethylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7-trimethyloct-1-ene. In another embodiment the alkyl-oolefins are selected from 4,4-dime- thylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trimethylhex-1-ene, 6,6-di- methylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7-trimethyloct-1-ene. In yet another embodiment, the alkyl-oolefin is 4,4-dimethylpent-1-ene. In yet another embodiment, the alkyl-oolefin is 5,5-dimethylhex-1-ene. In yet another embodiment, the alkyl-oolefin is 6,6-dime- thylhept-1-ene. In yet another embodiment, the alkyl-oolefin is 2,4,4-trimethylpent-1-ene. In yet another embodiment, the alkyl-oolefin is 2,5,5-trimethylhex-1-ene. In yet another embodiment, the alkyl-oolefin is 2,6,6-trimethylhept-1-ene. In yet another embodiment, the alkyl-oolefin is selected from 4,4-dimethylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trimethylhex-1- ene, 6,6-dimethylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7-trime- thyloct-1-ene.

In another embodiment, monomer II is a C6-Ci2 aryl-oolefins, such as styrol, and vinyl naphthalene. In yet another embodiment, monomer II is a mixed Ci-C2o alkyl-aryl-oolefins, such as omethylsty- rene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vi- nylxylene.

Further monomers which may be present in the polycarboxylic acid in polymerized form are, for example, halogenated C6-Ci2 aryl-oolefins, C6-Ci2 aryl-oolefins which bear nitro, alkoxy, haloalkyl, carbalkoxy, carboxy, amino and alkylamino groups, vinyl alcohol esters such as vinyl acetate, vinyl halides such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinylidene bromide, vinyl nitrile, vinyl carboxylates, 1-vinylamides such as 1-vinylpyrrolidone, 1-vi- nylpiperidone, 1-vinylcaprolactam, 1-vinylformamide, 1-vinylacetamide or 1-methyl-1-vinylacetamide, N-vinyl imidazole, Ci-C24-alkylesters and monosubstituted and disubstituted and unsubstituted Ci- to C24-alkylamides of monoethylenically unsaturated monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid, vinylsulfonic acid, unsaturated aldehydes such as acrolein, unsaturated ethers such as 1 ,4-cyclohexanedimethanol divinyl ether, 1 ,4-cyclohexanedimetha- nol monovinyl ether, butanediol divinyl ether, butanediol monovinyl ether, cyclohexyl vinyl ether, di- ethylene glycol divinyl ether, ethylene glycol monovinyl ether, ethyl vinyl ether, methyl vinyl ether, n- butyl vinyl ether, octadecyl vinyl ether, triethylene glycol vinyl methyl ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl dodecyl ether, vinyl tert-butyl ether, hexanediol divinyl ether, hexanediol monovinyl ether, diethylene glycol monovinyl ether, diethylami- noethyl vinyl ether, polytetrahydrofuran divinyl ether, tetraethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and aminopropyl vinyl ether. Usually, the polycarboxylic acid does not contain any further monomers in polymerized form.

In one embodiment, the polycarboxylic acid contains in polymerized form monomers I selected from C3-C8 ethylenically unsaturated monomers comprising carboxylic acid groups, and monomers II selected from ethylenically unsaturated monomers comprising a C1-C20 aliphatic, aromatic, or mixed aliphatic and aromatic group.

In another embodiment, the polycarboxylic acid contains in polymerized form monomers I selected from C3-C8 ethylenically unsaturated monomers comprising carboxylic acid groups, and monomers II selected from Ci-C2o alkyl-oolefins, C6-Ci2 aryl-oolefins, and mixed Ci-C2o alkyl-aryl-oolefins.

In another embodiment, the polycarboxylic acid contains in polymerized form monomers I selected from acrylic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fu- marie acid, mesaconic acid, or itaconic acid; and monomers II selected from C6-Cio alkyl-oolefins.

In another embodiment, the polycarboxylic acid contains in polymerized form maleic acid; and monomers II selected from ,4-dimethylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trimethylhex-1-ene, 6,6-dimethylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7-trimethyloct-1-ene.

The polycarboxylic acids of the above types are commercially available, or can be obtained by means of free-radical polymerization. However, it is also possible to employ other processes for the polymerization, for example controlled free-radical processes. The polymerization is carried out in the presence of the monomers and of one or more initiators and can be carried out with or without solvent, in emulsion or in suspension. The polymerization can be carried out as a batch reaction, as a semi-continuous operation or as a continuous operation. The reaction times are generally in the range of between 1 and 12 hours. The temperature range within which the reactions can be carried out is generally from 20 to 200°C, preferably from 40 to 120°C.

The initiators which are employed for the free-radical polymerization are customary free-radical- forming substances. Preferred is the initiator from the group of the heat-activatable polymerization initiators. These are initiators with a decomposition temperature in the range of from 20 to 180°C, in particular 50 to 120°C, preferred. Examples of suitable thermal initiators are inorganic peroxo com- pounds such as peroxodisulfates (ammonium and, preferably, sodium peroxodisulfate), peroxosul- fates, percarbonates and hydrogen peroxide; organic peroxo compounds such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis(o-toloyl)peroxide, succinyl peroxide, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl per- neodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and azobis(2-amidopropane) dihydrochloride. These initiators can be employed in combination with reducing compounds as initia- tor/regulator systems. Examples of such reducing compounds which may be mentioned are phosphorus-comprising compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-comprising compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxylate, and hydrazine.

Frequently, one also uses redox initiator systems, which consist of a peroxo compound, a metal salt and a reducing agent. Examples of suitable peroxo compounds are hydrogen peroxide, peroxodisul- fate (as the ammonium, sodium or potassium salt), peroxosulfates and organic peroxo compounds such as tert-butyl hydroperoxide, cumene hydroperoxide or dibenzoyi peroxide. Suitable metal salts are mainly iron(ll) salts such as iron(ll) sulfate heptahydrate. Suitable reducing agents are sodium sulfite, the disodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfona- toacetic acid, sodium hydroxymethanesulfinate, ascorbic acid, iso-ascorbic acid or mixtures of these.

It is preferred to employ thermal initiators, with inorganic peroxo compounds, in particular sodium peroxodisulfate, being preferred. It is especially advantageous to employ, as redox initiator system, the peroxo compounds in combination with sulfur- or phosphorus-comprising reducing agents, in particular sodium hydrogen sulfite or sodium hypophosphite.

The free-radical polymerization is preferably carried out in solution. Solvents are either one, or a combination of two or more, solvent(s). These are, for example, water, alcohols such as, for exam- pie, methanol, ethanol, isopropanol, dipolar-aprotic solvents such as, for example, DMF, DMSO or NMP, aromatic, aliphatic, halogenated or nonhalogenated hydrocarbons such as, for example, hex- ane, chlorobenzene, toluene or benzene. Preferred solvents are water, isopropanol, methanol, toluene, DMF, NMP, DMSO and hexane. Especially preferred are water and isopropanol. The mean mass molecular weight of the polycarboxylic acid is usually in the range from 1 ,000 to 15,000 g/mol, preferably from 5,000 to 10,000 g/mol. The mean mass molecular weight of the polycarboxylic acid is usually up to 12,000 g/mol, preferably up to 9,000 g/mol. The mean mass molecular weight of the polycarboxylic acid is usually at least 4,000 g/mol, preferably at least 6,000 g/mol. The mean mass molecular weight can be inter alia determined by gel filtration chromatography.

The concentration of the polycarboxylic acid in the premix may be from 0.01 to 20 wt%, preferably from 0.1 to 10 wt%, and most preferably from 0.1 to 5 wt%, based on the total weight of the premix. The concentration of the sulfosuccinate surfactant in the pesticide granules may be from 0.01 to 20 wt%, preferably from 0.1 to 10 wt%, most preferably from 1 to 5 wt%, and in particular from 2 to 6 wt%, based on the total weight of the pesticide granules.

The weight ratio of the polycarboxylic acid and the sulfosuccinate surfactant may usually range from 5: 1 to 1 : 10, preferably from 2: 1 to 1 :5, most preferably from 1 : 1 to 1 :3. The concentration of the mixture of the polycarboxylic acid and the sulfosuccinate surfactant in the premix may usually range from 1 to 20 wt%, preferably from 1 to 10 wt%, more preferably from 2 to 5 wt%, based on the total weight of the premix. The concentration of the mixture of the polycarboxylic acid and the sulfosuccinate surfactant in the pesticide granules may usually range from 1 to 20 wt%, preferably from 1 to 10 wt%, more preferably from 2 to 8 wt%, based on the total weight of the premix.

The pesticidal composition comprises a pesticide and a liquid. The term pesticide refers to at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators. Mixtures of pesticides are also suitable. In one embodiment, the pesticide is an insecticide. In another embodiment, the pesticide is a fungicide. In yet another embodiment the pesticide is a herbicide. Mixtures of pesticides of two or more of the above- mentioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, ben- zisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocar- bamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2- amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzo- furanones, methoxyacrylates, methoxycarba mates, morpholines, N-phenylcarbamates, oxazoli- dinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetam- ides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylme- thylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocar- bamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, tria- zoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphe- noxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phe- nylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenyl- carbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoro- amidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarbox- ylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadia- zoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, tria- zolopyrimidines, triketones, uracils, ureas. In one embodiment, the pesticide is a herbicide, preferably Bentazon. The term pesticide usually also relates to mixtures of compounds, and/or their salts. In one embodiment, the pesticide is in the form of a salt. The water-solubility of the pesticide at 25 °C is usually at least 10 g/l, preferably at least 50 g/l, and most preferably at least 100 g/l. The premix may contain at least 10 wt% of the pesticide, preferably at least 20 wt%, based on the total weight of the premix. The pesticide granules may contain at least 20 wt% of the pesticide, preferably at least 30 wt%, based on the total weight of the granules. The pesticide granules may contain from 10 to 80 wt% of the pesticide, preferably from 20 to 60 wt% of the pesticide, more preferably from 30 to 60 wt% of the pesticide, based on the total weight of the pesticide granules.

The weight ratio of the pesticidal composition to the mixture of the sulfosuccinate surfactant and the polycarboxylic acid may range from 100: 1 to 1 : 1 , preferably from 50: 1 to 5: 1 .

The liquid may be water, or an organic solvent. Organic solvents may relate to mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; halogenated hydrocarbons, e.g. chloroform, dichloromethane, chloromethane; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. acetone, cy- clohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; nitriles, e.g. ac- etonitrile; ethers, e.g. dimethylether, and tertbutyl ethyl ether; and mixtures thereof.

In one embodiment, the liquid does not contain organic solvents with a water-solubility at 25 °C below 1 g/l, preferably below 10 g/l.

In one embodiment, the liquid is a protic solvent, such as water, or an alcohol, preferably water. The premix may contain at least 10 wt% of the liquid, preferably at least 20 wt%, more preferably at least 25 wt% of the liquid. The liquid may have a dynamic viscosity at 25 °C of at least 0.1 mPas, preferably at least 0.5 mPas, and most preferably at least 0.8 mPas. The dynamic viscosity may be measured by standard test methods, e.g. ASTM D7042-14.

The pesticide is usually dispersed, or dissolved in the liquid. Preferably, the pesticide is dissolved in the liquid. Suitable formulation types of the pesticidal composition are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), or capsules (e.g. CS, ZC),. These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6^th Ed. May 2008, CropLife International.

The pesticidal composition usually comprises from 5 to 99 wt% of the liquid, preferably 10 to 95 wt%, more preferably 30 to 95, and in particular 40 to 80 wt% of the liquid, based on the total weight of the pesticidal compositions. The pesticidal composition may contain up to 95 wt% of the liquid, prefera- bly up to 90 wt%, most preferably up to 85 wt%, based on the total weight of the pesticidal composition.

The pesticidal composition usually comprises not more than 80 wt% of the pesticide, preferably not more than 70, most preferably not more than 60 wt%, and in particular not more than 55 wt%, based on the total weight of the pesticidal composition.

Usually, the premix comprises at least 20 wt% of the pesticidal composition, preferably at least 30 wt%, and most preferably at least 40 wt% of the pesticidal composition, based on the total weight of the premix. The premix may comprise up to 70 wt% of the pesticidal composition, preferably up to 60 wt%, based on the total weight of the premix. The premix usually comprises from 10 to 80 wt% of the pesticidal composition, preferably 20 to 70 wt%, more preferably 40 to 60 wt%, based on the total weight of the premix. The premix may contain at least 10 wt% of the liquid, preferably at least 20 wt%, based on the total weight of the premix. The premix may contain up to 60 wt% of the liquid, preferably up to 50 wt%, most preferably up to 30 wt%, based on the total weight of the premix. The premix usually contains from 5 to 90 wt% of the liquid, preferably 10 to 70 wt%, more preferably 10 to 50 wt% of the liquid, based on the total weight of the premix.

Advantageously, it is not necessary to add another process step for liquid removal before the premix is extruded, e.g. drying the premix, thereby saving time, costs, and energy. Instead, the extrusion process is characterized by high yields even if the liquid is still present in the premix at the concentrations and prefered concentrations given above. The premix is typically homogenized prior to extrusion by mixing, kneading, or other standard techniques. Notwithstanding the particulate form of some components, the term "homogenized" refers to a situation in which all components are evenly distributed in the premix. In particular, neither the sul- fosuccinate surfactant nor the polycarboxylic acid are coated on the surface of the solid carrier in a previous step, nor are they applied as coating on the solid carriers when preparing the premix.

The pesticide granules usually do not contain the liquid, but at most up to 5 wt%, preferably up to 1 wt% of the total weight of the pesticide granules.

In one embodiment, the premix comprises

a) the mixture of bentonite and silicates;

b) the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and

c) the pesticidal composition comprising the pesticide, and the liquid;

wherein the premix comprises from 20 to 40 wt% of the bentonite and from 10 to 30 wt% of the silicates, based on the total weight of the premix.

In one embodiment, the premix comprises

a) the mixture of bentonite and silicates;

c) the pesticidal composition comprising the pesticide, and the liquid; wherein the premix comprises from 20 to 35 wt% of the bentonite and from 10 to 25 wt% of the silicates, based on the total weight of the premix; and

wherein the weight ratio of the bentonite to the silicates is from 5:1 to 1 :2 In one embodiment, the premix comprises

a) the mixture of bentonite and silicates;

b) the mixture of an ester of sulfosuccinate, with octanol or its isomers; and the polycarboxylic acid; and

c) the pesticidal composition comprising the pesticide, and the liquid;

wherein the premix comprises from 20 to 35 wt% of the bentonite and from 10 to 25 wt% of the silicates, based on the total weight of the premix; and

wherein the weight ratio of the bentonite to the silicates is from 5:1 to 1 :2.

In one embodiment, the premix comprises

a) the mixture of bentonite and silicates;

b) the mixture of an ester of sulfosuccinate, with octanol or its isomers; and the polycarboxylic acid selected from copolymers comprising monomers I, and monomers II; and

c) the pesticidal composition comprising the pesticide, and water;

wherein the premix comprises from 20 to 35 wt% of the bentonite and from 10 to 25 wt% of the sili- cates, based on the total weight of the premix; and

wherein the weight ratio of the bentonite to the silicates is from 5:1 to 1 :2.

In one embodiment, the premix comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising in polymerized form monomers I selected from acrylic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, mesaconic acid, and itaconic acid; and

monomers II selected from Ci-Cio alkyl-a-olefin, C6-Ci2 aryl-a-olefins, and Ci-C2o alkyl-aryl-oolefins; and

c) the pesticidal composition comprising the pesticide, and the liquid. In one embodiment, the premix comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising maleic acid and the Ci-Cio alkyl-a-olefin in polymerized form; and

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising maleic acid and the Ci-Cio alkyl-a-olefin in polymerized form; and c) the pesticidal composition comprising the pesticide with the water-solubility at 25 °C of at least 10 g/l, and at least 20 wt% of the liquid, based on the total weight of the premix.

In one embodiment, the premix comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

c) the pesticidal composition comprising the pesticide with the water-solubility at 25 °C of at least 10 g/l, and at least 20 wt% of water, based on the total weight of the premix.

In one embodiment, the premix comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising maleic acid and the C1-C10 alkyl-oolefin in polymerized form; and

c) the pesticidal composition comprising the pesticide with the water-solubility at 25 °C of at least 10 g/l, and at least 20wt% of water, based on the total weight of the preimix. In one embodiment, the premix comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising in polymerized form maleic acid and the C1-C10 alkyl-oolefin selected from 4,4-dimethylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trime- thylhex-1-ene, 6,6-dimethylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7- trimethyloct-1-ene; and

a) the solid carrier selected from inorganic, and organic inert materials;

b) from 1 to 10 wt% of the mixture of the ester of sulfosuccinate, with octanol or its isomers;

a) 5 to 80 wt% of the solid carrier selected from inorganic, and organic inert materials;

b) 1 to 20 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) 10 to 80 wt% of the pesticidal composition comprising the pesticide, and the liquid. In one embodiment, the premix comprises

a) 50 to 65 wt% of the solid carrier selected from inorganic, and organic inert materials;

b) 1 to 20 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) 10 to 80 wt% of the pesticidal composition comprising the pesticide, and the liquid.

In one embodiment, the premix comprises

b) 1 to 10 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) at least 40 wt% of the pesticidal composition;

wherein the pesticidal composition comprises up to 60 wt% of the pesticide, based on the total weight of the pesticidal composition

In one embodiment, the premix comprises

b) 1 to 10 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) at least 10 wt% of the liquid; and

d) at least 20 wt% of the pesticide.

In one embodiment, the premix comprises

a) 30 to 80 wt% of the solid carrier selected from inorganic, and organic inert materials;

b) 1 to 20 wt% of the sulfosuccinate surfactant, 0.5 to 15 wt% of the polycarboxylic acid; and c) 10 to 50 wt% of the pesticide, and 10 to 50 wt% of the liquid.

In one embodiment, the premix comprises

a) 20 to 40 wt% of bentonite, 10 to 30 wt% of silicates;

b) 1 to 10 wt% of the sulfosuccinate surfactant, 0.1 to 5 wt% of the polycarboxylic acid; and c) at least 30 wt% of the pesticide, and at least 20 wt% of the liquid.

In one embodiment, the pesticide granules comprise

a) 20 to 75 wt% of the solid carrier selected from inorganic, and organic inert materials;

b) 0.5 to 10 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) 10 to 80 wt% of the pesticide.

In one embodiment, the pesticide granules comprise

b) 2 to 6 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) 30 to 60 wt% of the pesticide.

In one embodiment, the pesticide granules comprise

a) 20 to 50 wt% of bentonite, and 10 to 35 wt% of silicates;

In one embodiment, the pesticide granules comprise a) 20 to 50 wt% of bentonite, and 15 to 35 wt% of silicates;

b) 2 to 6 wt% of the mixture of the sulfosuccinate surfactant, and the polycarboxylic acid; and c) 30 to 60 wt% of the pesticide. In one embodiment, the pesticide granules comprise

a) a mixture of bentonite and silicates;

b) a mixture of the sulfosuccinate surfactant and the polycarboxylic acid; and

c) a pesticide. In one embodiment, the pesticide granules comprise

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

c) the pesticide.

In one embodiment, the pesticide granules comprise

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

and the polycarboxylic acid comprising in polymerized form maleic acid and the Ci-Cio alkyl-a-olefin selected from 4,4-dimethylpent-1-ene, 2,4,4-trimethylpent-1-ene, 5,5-dimethylhex-1-ene, 2,5,5-trime- thylhex-1-ene, 6,6-dimethylhept-1-ene, 2,6,6-trimethylhept-1-ene, 7,7-dimethyloct-1-ene, and 2,7,7- trimethyloct-1-ene; and

c) the pesticide.

In one embodiment, the pesticide granule comprises

a) the solid carrier selected from inorganic, and organic inert materials;

b) the mixture of the ester of sulfosuccinate, with octanol or its isomers;

c) the pesticide. The extrudate may be granulated in step 3). Granulation is commonly known to the skilled person, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Based on the extrusion process, the granules may have the shape of an extrudate. In the case of circular holes of the extruder, the spaghetti-shaped extrudate may be cut into cylindrical shape. In case of polygonal holes (e.g. triangular or rectangular), the extrudate may be cut into corresponding shapes. The resulting pellets might be broken into shorter granules. Preferably, the resulting gran- ules have cylindrical shape with a length of 0.2 to 10 mm and a diameter of 0.2 to 10 mm. More preferably, the resulting granules have cylindrical shape with a length of 0.5 to 10 mm and a diameter of 0.5 to 10 mm. The stick-like extrudate may be cut, e.g. with a rotating knife, into shorter sticks before or after drying, preferably before drying. In the case of circular holes, the spaghetti-shaped extrudate may be cut into cylindrical shape. In case of polygonal holes (e.g. triangular or rectangular), the extrudate may be cut into corresponding shapes. The resulting pellets might be broken into shorter granules before or after drying, preferably after drying. Optionally, in step d) the drying the extrudate resulting from step c) may be performed by conventional drying means, such as by heated air or vacuum.

Drying may be done by the application of elevated temperatures, such as hot air, from 30 to 150 °C, preferably from 50 to 80 °C. The heating time usually depends on the temperature, the size of the extrudate and the desired amount of liquid in the final product. The pesticide granules, or the premix, may contain further auxiliaries. Suitable auxiliaries are surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, com- patibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable surfactants are surface-active compounds, such as anionic, cationic, non-ionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutch- eon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, di- phenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl- naphthalenes, or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable non-ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A- B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polybases. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity them- selves, and which improve the biological performance of the compound I 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.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

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

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

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

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).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacry- lates, biological or synthetic waxes, and cellulose ethers.

When employed in plant protection, the amounts of pesticide applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, pesticide in an amount from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amount of pesticide applied de- pends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

The invention also relates to pesticide granules that are obtainable by the process for manufacturing pesticide granules, as described above. The invention furthermore relates to pesticide granules comprising a solid carrier selected from inorganic, and organic inert materials; a mixture of a sulfosuc- cinate surfactant, and a polycarboxylic acid; and a pesticide.

The invention also relates to a method of controlling undesired insect or mite attack, harmful fungi, and/or undesired vegetation, and/or for regulating the growth of plants, wherein the pesticide granules, or pesticide granules obtainable by the process for manufacturing pesticide granules, are allowed to act on the respective pests, their environment, or the crop plants to be protected from the respective pest, on the soil, and/or on the crop plants, and/or on their environment. The invention further relates to the use of the mixture comprising the sulfosuccinate surfactant, and the polycarboxylic acid, for preparing pesticide granules.

Advantages: the invention provides a process for manufacturing pesticidal granules, wherein higher amounts of pesticidal compositions comprising a liquid can be incorporated. The yield of manufactur- ing granules prepared from a premix with high contents of liquid is increased. High-payload granules containing a pesticide, which is available only in diluted form in a liquid, can be produced.

The following examples illustrate the invention without limiting its scope: Examples:

Bentazon: 50 wt% aqueous solution of the sodium salt of bentazon

Sulfosuccinate surfactant: branched Cs-alkyl diester of sodium sulfosuccinate

Polycarboxylate: Copolymer of maleic acid with a Cs alkyl-oolefin, mean average molecular weight

8000 g/mol.

Example 1 :

Granules GR-1 to GR-6 were produced. The ingredients as listed in Table 1 , except for bentazon (aqueous composition comprising 50 wt% of the sodium salt of bentazon), were mixed with a blender. Then, bentazon was added, and the mixture was kneaded. The obtained kneaded material was extruded with a screen hole of 0.8 mm (KAR-75; Tsutsuki Scientific Instruments Co., Ltd.). After extrusion, the extrudate was cut into granules of 1.0-2.0 mm length by hand and dried at 80 °C for 20 minutes by a drying machine (FD-LAB-1 ; Powrex Corporation). Then, the sieving was conducted with a sieve of 1.2 mm and 0.55 mm of mesh size to remove large lumps and fine particles. The preparation scale was 300 grams. Finally, the amount of prepared sample was measured, and the preparation yield was calculated. Table 2 showed the composition of the pesticide granules.

Table 1 : Composition of premix

^* Comparative granules not according to the invention

Claims

1. Process for manufacturing pesticide granules, comprising the steps of

1) preparing a premix comprising

a) a mixture of bentonite and silicates;

b) a mixture of a sulfosuccinate surfactant and a polycarboxylic acid; and

c) a pesticidal composition comprising a pesticide and a liquid;

2) and subsequently extruding the premix;

wherein the weight ratio of bentonite to silicates is from 10:1 to 1 :10.

2. The process of claim 1 , wherein the pesticidal composition comprises not more than 70 wt% of the pesticide based on the total weight of the pesticidal composition. 3. The process according to claim 1 or 2, comprising a preceding step 0) of providing the pesticidal composition comprising a pesticide and a liquid;

4. The process according to any of claims 1 to 3 comprising a subsequent step 3), wherein the extrudate is granulated.

5. The process according to any of claims 1 to 4 comprising no liquid removal step before step 2).

6. The process according to any of claims 1 to 5, wherein the premix in step 1) comprises at least 30 wt% of the pesticidal composition.

7. The process according to any of claims 1 to 6, wherein the weight ratio of the pesticidal composition c) to the mixture b) ranges from 100:1 to 1 :1. 8. The process according to any of claims 1 to 7, wherein the premix in step 1) comprises at least 20 wt% of the liquid.

9. The process according to any of claims 1 to 8, wherein the pesticide is bentazon. 10. The process according to any of claims 1 to 9, wherein the liquid is water.

11. The process according to any of claims 1 to 10, wherein the premix in step 1) comprises

a) 30 to 80 wt% of the mixture of bentonite and silicates;

b) 1 to 20 wt% of the sulfosuccinate surfactant, 0.5 to 15 wt% of the polycarboxylic acid; and

c) 10 to 50 wt% of the pesticide, and 10 to 50 wt% of the liquid.

12. The process according to any of claims 1 to 11 , wherein the granules have a cylindrical shape with a length, and a diameter from 0.5 to 10 mm.

3. The process according to any of claims 1 to 12, wherein the polycarboxylic acid is a co-polymer of a monomer I selected from C3-C8 ethylenically unsaturated monomers comprising car- boxylic acid groups; and a monomer II selected from ethylenically unsaturated monomers comprising a C1-C20 aliphatic, aromatic, or a mixed aliphatic and aromatic group.

4. The process according to any of claims 1 to 13, wherein the pesticide is dissolved in the liquid.

5. Pesticide granules comprising

a mixture of bentonite and silicates;

a mixture of a sulfosuccinate surfactant, and a polycarboxylic acid; and

a pesticide;

wherein the weight ratio of bentonite to silicates is from 10:1 to 1 :10.