ES2856859T3 - Non-aqueous pesticide suspension comprising a water soluble solvent, an inorganic thickener and an alkoxylate - Google Patents

Abstract

A non-aqueous liquid composition comprising less than 5% by weight of water and comprising a pesticide in the form of suspended particles, at least 10% by weight of a water-soluble solvent, an inorganic thickener and an alkoxylate, where the thickener Inorganic comprises silica particles, wherein the composition comprises up to 10% by weight of a water-insoluble organic solvent.

Description

DESCRIPTION

Non-aqueous pesticide suspension comprising a water soluble solvent, an inorganic thickener and an alkoxylate

The present invention relates to a non-aqueous liquid composition comprising a suspended particulate pesticide, a water soluble solvent, an inorganic thickener and an alkoxylate. The present invention further relates to a non-aqueous liquid composition comprising a suspended particulate pesticide, a propylene glycol solvent, an inorganic thickener and an alkoxylated alkanol. The present invention relates to a non-aqueous liquid composition comprising a pesticide in suspended particulate form, a water-soluble solvent, an inorganic thickener and an alkoxylate, which is preferably insoluble in water. The present invention relates to a non-aqueous liquid composition comprising a pesticide in the form of suspended particles, where the water-soluble solvent can be a propylene glycol solvent and where the inorganic thickener comprises silica particles. It further refers to a method for the preparation of said composition, where the pesticide, the water-soluble solvent, the inorganic thickener, the alkoxylated alkanol, optionally the block polymer surfactant and optionally the cosurfactant are brought into contact. It also refers to a non-therapeutic method to control phytopathogenic fungi and / or unwanted plant growth and / or unwanted attack by insects or mites and / or to regulate plant growth, where said composition is allowed to act on particular pests. , its habitat or the plants to be protected from the particular pest, the soil and / or the unwanted plants and / or the useful plants and / or their habitat.

Agrochemical formulations in the form of aqueous suspensions are known and can contain large amounts of water as a continuous phase to suspend the pesticide particles. However, such aqueous formulations have various drawbacks, for example, they are not suitable for pesticides that degrade slowly in the aqueous phase; pesticides that have increased water solubility may not be suspended; formulation additives must be water soluble; or microbial growth is high in aqueous systems. The object of the present invention was to overcome these and other drawbacks.

Document US5906962 describes stable, concentrated, non-aqueous suspensions of water-soluble active principles, in particular for use in agriculture, where the solid particles are dispersed in a water-miscible organic solvent with the aid of a dispersion system comprising three components, namely, a nonionic polymeric viscosity modifying surfactant, an anionic surfactant and a nonionic surfactant having a bulky hydrophobic substituent group. One embodiment of the present invention is a non-aqueous liquid composition comprising less than 5% by weight of water and comprising a pesticide in suspended particulate form, at least 10% by weight of a water soluble solvent, an inorganic thickener and an alkoxylate, where the inorganic thickener comprises silica particles, where the composition comprises up to 10% by weight of water insoluble organic solvent. The water soluble solvent may comprise one or more of the following: propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, propylene carbonate, ethylene carbonate, butylene carbonate, and dimethyl sulfoxide. The alkoxylate, which is preferably insoluble in water, comprises one or more compound (s) that may comprise (a) ethoxylated and propoxylated C12-18 alcohols; (b) polyglycols based on ethylene oxide (s) and / or propylene oxide (s); and (c) polyalkylene oxide modified heptamethyltrisiloxane. The inorganic thickener can be silica. In another embodiment, the composition may further comprise a block polymer surfactant. The block polymer surfactant can be an alkoxylate block polymer, comprising polyethylene oxide and polypropylene oxide blocks. A further embodiment of the present application is a method for the preparation of the composition described in the present invention, where the pesticide, the water soluble solvent, the inorganic thickener, the water insoluble alkoxylate, optionally the block polymer surfactant and optionally the cosurfactant is contacted. A further embodiment of the present invention is a non-therapeutic method to control phytopathogenic fungi and / or unwanted plant growth and / or unwanted attack by insects or mites and / or to regulate plant growth, where the composition is allowed described herein acts on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or the unwanted plants and / or the useful plants and / or their habitat.

The object of the present invention was achieved by means of a non-aqueous liquid composition comprising a pesticide in the form of suspended particles, a water soluble solvent, an inorganic thickener and an alkoxylate, preferably an alkoxylated alkanol.

The composition is a liquid composition, which can be liquid at 20 ° C. The composition usually comprises a continuous liquid phase and a suspended solid phase. The liquid phase usually comprises the water soluble solvent, such as propylene glycol. The solid phase usually forms solid particles within the liquid phase. The solid phase usually comprises the pesticide particles.

The composition is a non-aqueous composition. The composition comprises less than 5% by weight, preferably less than 1% by weight and, in particular, less than 0.3% by weight of water. In another form the composition is essentially free of water.

The expression "soluble in water" or "hydrophilic" means that the compound can have a solubility in water at 20 ° C of at least 5 g / l, preferably at least 20 g / l, more preferably at least 50 g / l , in particular, at least 100 g / l.

The expression "insoluble in water" or "hydrophobic" means that the compound can have a solubility in water at 20 ° C of at least 100 g / l, preferably up to 50 g / l ° C, more preferably up to 20 g / l in particular up to 5 g / l.

The term pesticide usually refers to at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, protectants, biopesticides and / or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides, and growth regulators. Especially preferred pesticides are insecticides. Pesticide mixtures of two or more of the aforementioned classes can 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. Some suitable insecticides are the insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereystoxin analogs, diazohydrazine compounds , METI acarizides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, ethoxazole, diafenthiuron, propargite, tetradiphon, chlorophenapyr, DNOC, buprofezine, ziromazine, amitraz, hydramethylnon, acequinocyrimus, derivatives, rotuacrymone, or flinger. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzoisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl amide carboxyls, carboxylamides, carboxyamides of benzyl amides, carboxylamides, carboxyamides of benzyl amides, carboxylamides or carboxylamides of benzyl amides, carboxylamides or carboxylamides of benzyl amides, carboxylamides or carboxyamides of benzyl , cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) -pyrimidines, hydroxylazolinone, morgantosanilides, iscrylamidobamines, imuranidazoleanilides, inorganic substances phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, pyrazines, piperidines, prophalimides azinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenozolecarboxamides, triphenozoliumcarboxamides, triphenozolinone compounds. Suitable herbicides are herbicides from the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilones, diphenidyl isoxaolinines, dinitroanilones, diphenidyl isoxaolinines, ginitroanilones, dinithoxaolinines nitriles, N-phenyl-phthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoramidates, phosphorodithioates, phthalamaidenes, pyridimidioxylic acids, pyridimidinamides, pyridimidioxylic acids, pyridimidinamides, pyridimidioxylic acids, pyridimidazines, pyridioxyls ) benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolecarboxamides, traizolopyrimidines, uracilinas, tricetonas. Mixtures of different pesticides are also suitable.

In one form the pesticide is metaflumizone. In another form the pesticide is abamectin. In another form the pesticide is glyphosate acid. In another form the pesticide is dinotefuran. In another form the pesticide is broflanilide. In another form the pesticide is an active compound of formula I

where

R1 is H, C ¹ -C ² alkoxy or C ¹ -C ² -alkyl C ¹ -C ^2;

R2 is CH ³ or halomethyl;

R3 is CN, C ¹ -C ⁶ haloalkyl C ¹ -C ⁶ alkoxy C ¹ -C ² -alkyl C ¹ -C ^2, alkenyl and ^C2 - ^C6 alkynyl , C ² -C ^6, cycloalkyl C ³ - C ^6, C ⁵ -C ⁶ cycloalkenyl, alkoxy C ¹ -C ⁶ -alkyl, wherein the C atoms are unsubstituted, or are partially or completely substituted with Ra;

Ra is halogen, CN, C ¹ -C ² alkyl, C ¹ -C ² haloalkyl, alkoxy C ¹ -C ⁴ haloalkoxy C ¹ -C ^2;

R4 is C ¹ -C ⁴ alkyl or a group mentioned for R3; or

R3 and R4 may together form C ⁵ -C ⁶ cycloalkyl, which is unsubstituted, or is partially or completely substituted with Ra;

R5 is H or a group mentioned for R4.

Some suitable examples for the active compound of formula I are 1-isopropyl-N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1- (1,2-dimethylpropyl) -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N, 5-dimethyl-N-pyridazin-4-yl-1- (2,2,2-trifluoro-1-methylethyl) pyrazole-4-carboxamide; 1- [1- (1-cyanocyclopropyl) ethyl] -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-ethyl-1- (2-fluoro-1-methyl-propyl) -5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1- (1,2-dimethylpropyl) -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1- [1- (1-cyanocyclopropyl) ethyl] -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-methyl-1- (2-fluoro-1-methyl-propyl] -5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1- (4,4-difluorocyclohexyl) -N-ethyl- 5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or 1- (4,4-difluorocyclohexyl) -N, 5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide. Compounds are known from WO2010 / 034737, WO2012 / 084670, WO2012 / 143317 and WO2015 / 055497, respectively.

The pesticide may have a melting point of at least 40 ° C, at least 50 ° C, preferably at least 70 ° C and in particular at least 90 ° C.

The pesticide may have a solubility in water at 20 ° C of at least 0.5 g / l, preferably at least 2 g / l ° C, more preferably at least 10 g / l, and in particular at least 50 g / l. The pesticide can have a solubility in water at 20 ° C of up to 250 g / l, up to 250 g / l, up to 150 g / l or up to 80 g / l. In a preferred form the pesticide may have a solubility in water at 20 ° C of up to 10 g / l, up to 5 g / l, up to 1 g / l ° C or up to 0.5 g / l.

The pesticide can be present in the form of crystalline or amorphous particles that are solid at 20 ° C. The pesticide usually has a particle size distribution with a Dx50 value of 0.01 to 50 µm, 0.1 to 10 µm, preferably 0.2 µm to 5 µm, and especially preferably 0.5 µm. at 2 jm. The particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles. The preparation of the sample, for example dilution to the measurement concentration, will depend, in this measurement method, on the fineness and concentration of the active substances in the suspension sample and the apparatus used (e.g. Malvern Mastersizer ), among others. The procedure must be developed for the system in question and is known to a person skilled in the art.

The composition can comprise at least one additional pesticide in addition to the pesticide. The additional pesticide can be present in the form of suspended particles and / or in dissolved form. Preferably, the additional pesticide may be present in the form of suspended particles. In another preferred form the additional pesticide may be present in dissolved form. The additional pesticide can be selected from the list of pesticides mentioned above.

The composition may comprise 1 to 50% by weight, preferably 5 to 35% by weight, and in particular 10 to 30% by weight of the total sum of the pesticide and the additional pesticide. In another form the composition may comprise at least 0.1% by weight, preferably at least 1% by weight and in particular at least 10% by weight of the total sum of the pesticide and the additional pesticide.

The water soluble solvent can include one or more of the following: propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, propylene carbonate, ethylene carbonate, butylene carbonate, and dimethyl sulfoxide. In another form the water soluble solvent can comprise propylene glycol, ethylene glycol, polyethylene glycol or glycerin. In another form the water soluble solvent may comprise propylene glycol, polyethylene glycol or glycerin. Mixtures of different water soluble solvents are also suitable. The water soluble solvent preferably comprises propylene glycol (1,2-propylene glycol) or polyethylene glycol. The water soluble solvent comprises in particular propylene glycol (eg 1,2-propylene glycol).

The water-soluble solvent may have a solubility in water at 20 ° C of at least 10 g / l, preferably at least 50 g / l ° C, more preferably at least 100 g / l, and in particular at least 200 g / l.

The propylene glycol can be 1,2-propylene glycol or 1,3-propylene glycol. Preferably, the propylene glycol is 1,2-propylene glycol. Polyethylene glycol usually has a melting point of up to 25 ° C, preferably up to 20 ° C, and in particular up to 15 ° C. Polyethylene glycol usually has an average molar mass of up to 1000 g / mol, preferably up to 700 g / mol, and in particular up to 500 g / mol.

The composition comprises at least 10% by weight, and in particular at least 15% by weight of the water-soluble solvent. The composition may comprise 10 to 50% by weight, preferably 10 to 40% by weight, and in particular 10 to 30% by weight of the water-soluble solvent. In another form the composition may comprise 10 to 90% by weight, preferably 10 to 85% by weight, and in particular 15 to 80% by weight of the water soluble solvent. In another form the water soluble solvent is added in an amount to fill the composition to 100% by weight.

The sum of the amounts of the water-soluble solvent (for example, propylene glycol) and the alkoxylate (for example, alkoxyalized alkanol) is usually at least 25 % by weight, preferably at least 35 % by weight, and in particular at least 40% by weight of the composition.

The composition may comprise an additional organic solvent in addition to the water soluble solvent. Suitable additional organic solvents are medium to high boiling mineral oil fractions, eg kerosene, gas oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, eg benzyl alcohol, cyclohexanol; DMSO; ketones, for example cyclohexanone; esters, for example lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, eg, N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. The composition may comprise up to 10% by weight, preferably up to 3% by weight and, in particular, up to 1% by weight of the additional organic solvents. In one form the composition is essentially free of the additional organic solvent. Normally, the additional organic solvent is insoluble in water.

The inorganic thickener comprises particles.

Generally the silica is available as fumed silica and precipitated silica. Precipitated silica is typically produced by precipitation from a solution containing silicate salts, such as by reacting an alkali silicate solution with a mineral acid. Fumed silica (also known as fumed silica) is typically produced by flame pyrolysis of silicon tetrachloride or evaporated quartz sand in a hot electric arc of about 3000 ° C. Fumed silica and precipitated silica clearly differ in their chemical, physical and structural properties and are therefore used for different industrial purposes. For example, precipitated silica has many pores with a pore size of up to 30 nm, while fumed silica generally does not have such pores. The inorganic thickener can be selected from fumed silica particles that are preferably free of pores (eg, pores with a pore size of up to 30 nm). In general, the silica particles are available as hydrophilic silica particles or as hydrophobic modified silica particles. In general, silica is hydrophilic due to the silanol (Si-OH) groups on the surface of the particles. These silanol groups can be chemically reacted with various reagents to render the silica hydrophobic. Hydrophobic modified silica particles are usually modified by treatment with a silane, a siloxane, or a mixture thereof. Some examples of silanes or siloxanes are dimethyldichlorosilane, octamethylcyclotetrasiloxane, polydimethylsiloxane, octylsilane, hexamethyldisiloxane, methacrylsilane.

In the present invention the inorganic thickener is selected from fumed silica particles which are preferably hydrophilic silica particles. Preferably, the silica particles are not hydrophobic silica particles. Preferably the silica particles are not modified by treatment with a silane, a siloxane or a mixture thereof. Preferably the silica particles are free from modification by treatment with a silane, a siloxane or a mixture thereof. The composition can be essentially free of hydrophobic modified silica particles (eg, hydrophobic modified silica particles modified by treatment with a silane, a siloxane, or a mixture thereof).

Typically, the inorganic thickener contains particles (eg silica particles) with a specific surface area in the range of 50 to 500 m2 / g, preferably 100 to 350 m2 / g and, in particular, 170 to 230 m2 / g. . In another form the inorganic thickener contains silica particles with a specific surface area in the range of 50 to 600 m2 / g, preferably 140 to 450 m2 / g, and in particular 170 to 350 m2 / g. In another form the inorganic thickener contains silica particles with a specific surface area of at least 50 m2 / g, preferably at least 80 m2 / g, and in particular at least 120 m2 / g. The specific surface area can refer to the BET surface area. The specific surface area can be determined according to DIN ISO 9277.

In general, a distinction is made in the case of particles between primary and secondary particle diameter. A plurality of smaller particles (having a primary particle diameter) can agglomerate to form a larger particle (having a secondary particle diameter). The secondary particle diameter can therefore often be referred to as the agglomerate size.

Typically, the inorganic thickener contains particles (eg silica particles) with a primary particle diameter in the range 0.1 to 500 nm, preferably 1 to 100 nm, in particular 5 to 25 nm. The primary particle diameter is preferably determined by transmission electron microscopy (MET).

Usually, the pH value of an aqueous dispersion of the silica particles is in the range of 1 to 5.5, preferably in the range of 2 to 5.0, and in particular in the range of 3 to 4.8. . The pH value is usually determined as a 4% by weight dispersion of the silica particles in water.

The silica particles may comprise at least 95% by weight, preferably at least 98% by weight, and in particular at least 99.3% by weight of SiO ² .

The weight loss on ignition (also called ignition loss ) of the silica particles is up to 5 % by weight, preferably up to 4.0% by weight, and in particular up to 2.1% by weight. Loss of ignition can be determined at 1000 ° C (for example, 2 hours at 1000 ° C).

The composition may comprise up to 5% by weight, preferably up to 2.5% by weight and, in particular, up to 1.5% by weight of the inorganic thickener (eg silica particles). In another form the composition may comprise up to 1.5% by weight, preferably up to 1.0% by weight, and in particular up to 0.8% by weight of the inorganic thickener (eg silica particles). The composition may comprise from 0.01 to 5% by weight, preferably from 0.05 to 2.5% by weight and, in particular, from 0.1 to 1.5% by weight of the inorganic thickener (for example, particles silica). In another form the composition may comprise from 0.01 to 3.0% by weight, preferably from 0.05 to 1.0% by weight and, in particular, from 0.1 to 0.8% by weight of the inorganic thickener (for example, silica particles).

Suitable alkoxylates (eg, water insoluble alkoxylates) include, but are not limited to: polyglycols based on ethylene oxide (s) and / or propylene oxide (s); fatty oleyl alcohols and polyalkylene oxide modified peptamethyltrisiloxane. Preferably, the alkoxylate is an alkoxylated alkanol.

In another form some suitable alkoxylates include alkoxylated alkanols, which are usually C ¹ -C ²⁰ (preferably C ⁸ -C ²⁰ ) linear or branched alkoxylated, saturated or unsaturated alkanols, preferably C ² -C ¹⁸ alkanols (preferably C ⁸ -C ¹⁸ ) ethoxylated, ethoxylated and propoxylated or ethoxylated and butoxylated, linear or branched, saturated or more preferably, ethoxylated and propoxylated ^{C 4} -C ¹⁸ (preferably C ¹² -C ^{20) alkanols.} The alkanol unit of the alkoxylated alkanol can be a technical mixture of various chain lengths and isomers. The total number of alkoxy units in the alkoxylated alkanols can range from 5 to 30, preferably from 10 to 25 alkoxy units (eg ethyleneoxy and / or propyleneoxy units). The alkoxy units (eg EO and PO units) are preferably present in a block sequence, in particular as a diblock sequence. The polyalkoxylate chain of alkoxylated alkanols can be terminated with a hydroxy group or a C ¹ to C ⁴ alkyl, where the hydroxy group is preferred. In another form, the alkoxy units (eg EO and PO units) are preferably in a block sequence, in particular as a diblock sequence, and the polyalkoxylate chain of the alkoxylated alkanols is terminated with a hydroxy group.

In another form the preferred suitable alkoxylates are alkoxylated alkanols of formula (I)

Ra-O- (AO) m-R1 (I)

in which

Ra is a straight or branched chain alkyl or alkylene with 1 to 32, preferably 4 to 32, more preferably 10 to 22, carbon atoms,

AO is an ethylene oxide radical, propylene oxide radical, butylene oxide radical, pentylene oxide radical, styrene oxide radical, or mixtures of the above-mentioned radicals in random or block sequence (where a diblock sequence is preferred) ,

m are numbers from 1 to 30 and

R1 is hydrogen or alkyl with 1 to 4 carbon atoms.

Particularly preferred alkoxylated alkanols are those of formula (II)

Rb-O- (EO) p- (PO) q-R1 (II)

in which

Rb is a straight or branched chain alkyl or alkylene with 1 to 32, preferably 4 to 32, more preferably 10 to 22, particularly preferably 6 to 18, carbon atoms,

EO is -CH ² CH ² -O-,

PO is -CH ² -CH (CHa) -O- or - (CH ² ) aO-,

p are numbers from 1 to 20, preferably from 2 to 15,

q are numbers from 1 to 25, preferably from 5 to 20 and

R1 is hydrogen or alkyl with 1 to 4 carbon atoms,

where the EO and PO units can appear in random sequence or as blocks.

The alkoxylated alkanol can have a solidification temperature below 50 ° C, preferably below 20 ° C, and in particular below 0 ° C.

The composition may comprise at least 5% by weight, at least 10% by weight, preferably at least 15 % by weight and in particular at least 20 % by weight of the alkoxylate (for example the alkoxylated alkanol). In another form the composition may comprise at least 0.1% by weight, at least 0.5% by weight, preferably at least 1% by weight and, in particular, at least 1.5% by weight of the alkoxylate (for example, the alkoxylated alkanol). The composition may comprise 1 to 50% by weight, preferably 10 to 40% by weight, and in particular 20 to 35% by weight of the alkoxylate (for example, the alkoxylated alkanol).

In one form the alkoxylate is a short chain alkoxylated alkanol, which is an alkoxylated alkanol of formula I, wherein Ra is straight or branched chain alkyl with 1 to 8, preferably 2 to 6, and in particular 3 to 5 carbon atoms. In another form the alkoxylate is a short chain alkoxylated alkanol, which is an alkoxylated alkanol of formula II, wherein Rb is straight or branched chain alkyl with 1 to 8, preferably 2 to 6, and in particular 3 to 5 carbon atoms. The composition may comprise at least 0.1% by weight, at least 0.5% by weight, preferably at least 1% by weight and, in particular, at least 1.5% by weight of the alkoxylated alkanol of short chain. The composition may comprise from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight and, in particular, from 1 to 8% by weight of the short-chain alkoxylated alkanol.

The composition may comprise a block polymer surfactant. The block polymer surfactant can be a diblock polymer or a triblock polymer, where triblock polymer is preferred. The blocks of the block polymer surfactant can be of the AB or ABA type, where the ABA type is preferred. Typically, the block polymer surfactant is a nonionic surfactant.

The block polymer surfactant is preferably an alkoxylate block polymer, which may comprise polyethylene oxide and polypropylene oxide blocks. The alkoxylate block polymers usually comprise at least 20% by weight, preferably at least 30% by weight, of polymerized ethylene oxide. In a preferred form the alkoxylate block polymers comprise at least 10% by weight, preferably at least 15% by weight of polymerized ethylene oxide. The alkoxylate block polymers are preferably A-B-A type block polymers comprising blocks of polyethylene oxide (block "A") and polypropylene oxide (block "B"). Alkoxylate block polymers are usually terminated at both ends with hydroxyl groups.

The molecular weight of the block polymer surfactant (eg, the alkoxylate block polymer) can be 1000 to 30000 Da, preferably 2000 to 15000 Da.

The block polymer surfactant (for example, the alkoxylate block polymer) may have a solubility in water at 20 ° C of at least 3% by weight, preferably at least 5% by weight and in particular at less 8% by weight.

The block polymer surfactant (eg, the alkoxylate block polymer) may have an HLB value in the range of 8 to 22, preferably 10 to 20. In another form the block polymer surfactant (eg, the alkoxylate block polymer) may have an HLB value in the range of 1 to 10, preferably 1 to 8. HLB can be calculated by known methods.

In a preferred form the block polymer surfactant is an ABA type alkoxylate block polymer comprising blocks of polyethylene oxide (block "A") and polypropylene oxide (block "B") and wherein the block polymer Alkoxylate is terminated at both ends with hydroxyl groups.

The composition may comprise at least 7% by weight, preferably at least 12% by weight, and in particular at least 18% by weight of the block polymer surfactant (eg, the alkoxylate block polymer). In another form the composition may comprise at least 3% by weight, preferably at least 5% by weight and, in particular, at least 10% by weight of the block polymer surfactant (for example, the block polymer alkoxylate). The composition may comprise 5 to 40% by weight, preferably 10 to 35% by weight, and in particular 15 to 30% by weight of the block polymer surfactant (for example, the alkoxylate block polymer). In another form the composition may comprise 1 to 40% by weight, preferably 5 to 35% by weight, and in particular 10 to 30% by weight of the block polymer surfactant (for example, the block polymer alkoxylate).

The sum of the amounts of the water-soluble solvent, the alkoxylate and the block polymer surfactant is usually at least 40% by weight, preferably at least 50% by weight, and in particular at least 60% by weight. of the composition.

The composition can comprise a nonionic cosurfactant. It can have an HLB value in the range of 6 to 16, preferably 8 to 16, and in particular 8 to 14. HLB can be calculated by known methods. Suitable cosurfactants are phenol alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, and mixtures thereof. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are the esters of acids fatty acids, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose glucose esters, or alkylpolyglucosides. The cosurfactant is usually different from the block polymer surfactant.

A preferred nonionic cosurfactant is a phenol alkoxylate, preferably a polyarylphenol alkoxylate, more preferably a polyarylphenol ethoxylate, and in particular a tristyrylphenol ethoxylate. The phenol alkoxylate may comprise at least 1 to 70, preferably 3 to 40, and in particular 5 to 30 alkylene oxide units (preferably ethylene oxide units). Phenol alkoxylate usually has an HLB value in the range of 7 to 17, preferably 9 to 17, and in particular 11 to 15.

The composition may comprise at least 3% by weight, preferably at least 7% by weight, and in particular at least 12% by weight of the nonionic cosurfactant (eg phenol alkoxylate, preferably polyarylphenol alkoxylate). The composition may comprise 1 to 35% by weight, preferably 5 to 25% by weight, and in particular 10 to 20% by weight of the nonionic cosurfactant (eg phenol alkoxylate, preferably polyarylphenol alkoxylate).

The composition may comprise additional surfactants in addition to the nonionic cosurfactant and the block polymer surfactant. Examples of other surfactants are listed in McCutcheon's, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. Or North American Ed.). Additional surfactants can be anionic surfactants and cationic surfactants, where anionic surfactants are preferred.

Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodebyl and tridecyl sulfonates sulfonates. and alkylnaphthalenes, sulfosuccinates, 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 alkyl phenol ethoxylates.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups or long chain primary amine salts.

The additional surfactant is preferably an anionic surfactant selected from sulfonates or sulfates, where sulfonates are preferred. The additional surfactant is preferably selected from alkylaryl sulphonates, diphenylsulphonates, alpha-olefin sulphonates, lignin sulphonates, fatty acid and oil sulphonates, ethoxylated alkylphenol sulphonates, alkoxylated arylphenol sulphonates, condensed naphthalene sulphonates, and docyl benzene sulphonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates, or of sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols or of fatty acid esters. The additional surfactant is more preferably selected from alkylarylsulfonates, condensed naphthalene sulfonates, naphthalene sulfonates and alkylnaphthalenes, where condensed naphthalene sulfonates are preferred.

The composition may comprise 0.1 to 15% by weight, preferably 1 to 10% by weight and, in particular, 2 to 8% by weight of the additional surfactants (for example, the anionic surfactant, preferably selected from sulfonates or sulfates).

In one form the alkoxylate is a short chain alkoxylated alkanol and the composition comprises less than 5% by weight, preferably less than 1% by weight and, in particular, less than 0.1% by weight of the block polymer surfactant ( for example, alkoxylate block polymer). In another form the alkoxylate is a short chain alkoxylated alkanol and the composition is essentially free of the block polymer surfactant (eg, the alkoxylate block polymer).

In one form the alkoxylate is a short chain alkoxylated alkanol and the composition comprises an additional surfactant, preferably selected from anionic surfactants (eg, sulfonates or sulfates). In another form the alkoxylate is a short chain alkoxylated alkanol of formula I, wherein Ra is straight or branched chain alkyl or alkylene with 1 to 8, preferably 2 to 6, and in particular 3 to 5 carbon atoms. carbon and the composition comprises an additional surfactant selected from alkylarylsulfonates, condensed naphthalene sulfonates, naphthalene sulfonates, and alkylnaphthalenes, where condensed naphthalene sulfonates are preferred.

In another form the alkoxylate is a short chain alkoxylated alkanol, wherein the composition comprises 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and in particular 1 to 8% by weight of the short chain alkoxylated alkanol and the composition comprises an additional surfactant, preferably selected from surfactants anionic compounds (eg sulfonates or sulfates) and the composition comprises 0.1 to 15 % by weight, preferably 1 to 10% by weight, and in particular 2 to 8% by weight of the additional surfactant. In one form the alkoxylate is a short chain alkoxylated alkanol and the composition comprises an additional surfactant, preferably selected from anionic surfactants (eg, sulfonates or sulfates), and the composition is essentially free of the block polymer surfactant (eg, alkoxylate block polymer).

The composition can comprise additional auxiliaries. Some examples of suitable auxiliary products are antifoaming agents, colorants, adhesives and binders. Some suitable antifoaming agents are silicones, long chain alcohols, and fatty acid salts. Some suitable colorants (eg red, blue or green) are low water solubility pigments and water soluble dyes. Some examples are inorganic colorants (eg, iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (eg, alizarin-, azo-, and phthalocyanine dyes). Some suitable adhesive or binding agents are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The composition can be used for the treatment of plant propagation materials, particularly seeds. The compositions in question give, after a dilution of two to ten times, concentrations of the active principle of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in ready-to-use preparations. The application can be done before or during sowing. Some methods of applying or treating the compositions thereof, respectively, on the plant propagation material, especially the seeds include coating, coating, granulating, dusting, wetting and methods of applying the propagation material in the furrow. Preferably, the composition is applied to the plant propagation material by a method in such a way that germination is not induced, for example by coating, granulating, coating and dusting. When used in plant protection, the amounts of pesticide applied are, depending on the type 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, in particular 0.1 to 0.75 kg per ha. In the treatment of plant propagation materials such as seeds, for example by dusting, coating or macerating the seed, amounts of active ingredient of 0.1 to 1000 g are generally required, preferably 1 to 1000 g, more preferably 1 to 100 g and most preferably 5 to 100 g, per 100 kilograms of plant propagation material (preferably seeds).

The user applies the composition according to the invention usually from a pre-dosing device, a spray backpack, a spray tank, a spray plane or an irrigation system. Usually, the composition is composed of water, buffer and / or additional auxiliaries at the desired application concentration and the ready-to-use spray liquor or agrochemical composition according to the invention is thus obtained. Typically, 20 to 2000 liters, preferably 50 to 400 liters, of ready-to-use spray are applied per hectare of useful agricultural area.

The present invention further relates to a non-therapeutic method to control phytopathogenic fungi and / or the unwanted growth of plants and / or the unwanted attack of insects or mites and / or to regulate the growth of plants, where it is allowed to the composition acts on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and / or on unwanted plants and / or on the crop plants and / or on their environment.

Some examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, barley or rice; beets, for example sugar beets or fodder beets; pommel fruits, stone fruits and soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, gooseberries or gooseberries; legumes, for example beans, lentils, peas, alfalfa or soybeans; oil crops, eg oilseed rape, mustard, olives, sunflowers, coconut, cocoa, castor beans, oil palm, peanuts or soybeans; cucurbits, for example giant gourds / gourds, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruits, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, giant squash / squash or peppers; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial raw material crops, eg corn, soybeans, wheat, oilseed rape, sugar cane or palm oil; corn; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for winemaking); hops; herbs, for example grass; stevia ( Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and the products harvested from these plants.

The term "crop plants" also includes those plants that have been modified by crossing, mutagenesis or recombinant methods, including biotechnological agricultural products that are on the market or under development. Genetically modified plants are plants whose genetic material has been modified in a way that does not occur under natural conditions by hybridization, mutations, or natural recombination (ie, recombination of genetic material). In this case, one or more genes, as a rule, will be integrated into the genetic material of the plant to improve the properties of the plant. Such recombinant modifications also they comprise post-translational modifications of proteins, oligo- or polypeptides, for example, by glycosylation or binding polymers such as, for example, prenylated, acetylated or farnesliated moieties or PEG moieties. The present invention further relates to seeds containing the composition.

The present invention offers several advantages: Due to the low water content the composition is suitable for formulating pesticides that are sensitive to water; pesticides that have increased water solubility can be suspended; microbial growth is reduced; storage stability is high; freeze-thaw stability is high; it is easier to incorporate adjuvants (eg alkoxylates) into the formulation; and the effectiveness of the composition is improved.

The examples that follow illustrate the invention without imposing any limitation.

Examples

Chemical stabilizer: liquid alkaline organic amine compound.

Sulfonate A: Sodium alkylnaphthalenesulfonate formaldehyde polycondensate, water soluble powder.

Thickener: Untreated hydrophilic white powder fumed silica, specific surface area (BET) about 200 m2 / g; average primary particle diameter 12 nm, bulk density about 0.05 kg / m3, pH in water (4% by weight) about 3.8 to 4.6; loss of ignition (1000 ° C) up to 1.0% by weight; loss on drying up to 1.5% by weight; SiO ² content at least 99.8% by weight.

Alkoxylate A: Short chain alkoxylated alkanol, ethoxylated and propoxylated nonionic butanol (diblock sequence) with HLB of 17, cloud point approximately 75 ° C, melting point approximately 30 to 35 ° C. Alkoxylate B: ethoxylated and propoxylated nonionic liquid C12-18 aliphatic alcohol (diblock sequence), insoluble in water, soluble in alcohols, solidification temperature about -5 to -8 ° C.

Cosurfactant A: Nonionic ethoxylated tristyrylphenol surfactant, HLB 10-11.

Block polymer A: non-ionic EO-PO-EO triblock copolymer, average molecular weight about 6000 Da, ethylene oxide (EO) content about 40% by weight, melting point about 30-33 ° C, HLB 12-18, solubility in water at least 10% by weight at 25 ° C.

Insecticide A: 1- (1,2-dimethylpropyl) -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide

Insecticide B: 1- [1- (1-cyanocyclopropyl) ethyl] -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide

Insecticide C: N-ethyl-1 - [(1S, 2S) -2-fluoro-1-methyl-propyl] -5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide

Example 1: Suspension of metaflumizone in continuous phase of polyethylene glycol

A liquid suspension of metaflumizone was prepared having the following composition:

The pesticide suspension was prepared by the following procedure:

1. Add metaflumizone, Sulfonate A, in Polyethylene Glycol (average molecular weight 400) while stirring. Continue stirring until smooth.

2. The above mixture was then wet milled using a bead mill to a particle size of about 2 µm.

3. Add Thickener to the previous mixture, mix until uniform.

Three prepared samples were stored under the following conditions: (a) one sample was stored at -10 ° C, (b) Another sample was stored at F / T (daily cyclical temperature -10 ° C to 30 ° C) and (c) a third sample was stored at 54 ° C for two weeks. Particle size was measured before / after storage by Malvern Mastersizer 2000.

The stability of the suspension was determined by visual observation of the phase separation of the sample after storage, as well as the increase in particle size before / after storage at different storage temperatures. It was found that there is no increase in particle size at all the above storage temperatures and no phase separation occurred, therefore, the metaflumizone suspension was physically stable.

Example 2: Abamectin Suspension in Propylene Glycol Continuous Phase

An abamectin suspension was prepared with the following composition:

The pesticide suspension was prepared by the following procedure:

1. Add Abamectin, Co-Surfactant A, Block Polymer A, Alkoxylate B in the propylene glycol while stirring. Continue stirring until smooth.

2. The above mixture was then wet milled using a bead mill to a particle size of about 2 µm.

3. Add Thickener to the previous mixture, mix until uniform.

Three samples were stored and analyzed as described in Example 1. It was found that there is no increase in particle size at all of the above storage temperatures and no significant phase separation occurred, hence the abamectin suspension he was physically stable.

Example 3: Suspension of glyphosate acid

A mixture of Dicamba Na salt and glyphosate acid was prepared having the following composition:

The pesticide suspension was prepared by the following procedure:

1. Add Dicamba Na, Sulfonate A, Stabilizer in 1,2-propylene glycol while stirring. Continue stirring until Dicamba Na dissolves completely.

2. Add glyphosate acid to the above mixture while stirring. Continue stirring until smooth. 3. The above mixture was then wet milled using a bead mill to a particle size of about 2 µm.

4. Add Thickener to the previous mixture, mix until uniform.

Three samples were stored and analyzed as described in Example 1. It was found that there is no increase in particle size at all of the above storage temperatures and no phase separation occurred, therefore the suspension was physically stable. .

Example 4: Suspension of metaflumizone in propylene glycol

Aphidopyropene and formulation additives (except thickener) were added to 1,2-propylene glycol while stirring. Stirring was continued until the apidopyropene was completely dissolved. Then metaflumizone and Thickener were added to the mixture while stirring. Stirring was continued until homogeneous. The mixture was then wet milled using a bead mill to a particle size of about 2 µm.

Samples were stored and analyzed as in Example 1. It was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 5: Suspension of dinotefuran in propylene glycol

Aphidopyropene and formulation additives (except thickener) were added to 1,2-propylene glycol while stirring. Stirring was continued until the apidopyropene was completely dissolved. Dinotefuran and Thickener were then added to the mixture while stirring. Stirring was continued until homogeneous. The mixture was then wet milled using a bead mill to a particle size of about 2 µm.

Samples were stored and analyzed as in Example 1. It was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 6: Suspension of dinotefuran in propylene glycol

Aphidopyropene and formulation additives (except thickener) were added to 1,2-propylene glycol while stirring. Stirring was continued until the apidopyropene was completely dissolved. Dinotefuran and Thickener were then added to the mixture while stirring. Stirring was continued until homogeneous. The mixture was then wet milled using a bead mill to a particle size of about 2 µm.

Samples were stored and analyzed as in Example 1. It was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 6: Suspension of broflanilide in propylene glycol

Aphidopyropene and formulation additives (except thickener) were added to 1,2-propylene glycol while stirring. Stirring was continued until the apidopyropene was completely dissolved. Broflanilide and Thickener were then added to the mixture while stirring. Stirring was continued until homogeneous. The mixture was then wet milled using a bead mill to a particle size of about 2 µm.

Samples were stored and analyzed as in Example 1. It was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 7: Suspension of broflanilide and Insecticide A in propylene glycol

Broflanilide, Insecticide A, and all formulation additives were added to 1,2-propylene glycol while stirring. Stirring was continued until homogeneous. The mixture was then wet milled using a bead mill to a particle size of about 2 µm.

Samples were stored and analyzed as in Example 1. It was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 8: Suspension of Broflanilide and Insecticide B in Propylene Glycol

Example 7 was repeated with Insecticide B instead of Insecticide A. Again, it was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Example 9: Suspension of broflanilide and Insecticide C in propylene glycol

Example 7 was repeated with Insecticide C instead of Insecticide A. Again, it was found that there was no increase in particle size at all storage temperatures and no phase separation occurred, therefore the suspension was physically stable.

Claims (15)

1. A non-aqueous liquid composition comprising less than 5 % by weight of water and comprising a pesticide in suspended particulate form, at least 10% by weight of a water-soluble solvent, an inorganic thickener and an alkoxylate, where the inorganic thickener comprises silica particles, wherein the composition comprises up to 10% by weight of a water-insoluble organic solvent. 2. The composition according to claim 1, wherein the water soluble solvent comprises one or more of the following: propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, propylene carbonate, ethylene carbonate, butylene carbonate and dimethyl sulfoxide. 3. The composition according to claims 1 to 2 comprising at least 10% by weight of the alkoxylate. 4. The composition according to claims 1 to 3, wherein the alkoxylate is an alkoxylated alkanol. The composition according to any one of claims 1 to 4, wherein the sum of the amounts of the water soluble solvent and the alkoxylate is at least 40% by weight of the composition. 6. The composition according to any of claims 1 to 5, comprising up to 5.0% by weight of the inorganic thickener. The composition according to any one of claims 1 to 6, further comprising a block polymer surfactant. The composition according to any of claim 7, comprising at least 5% by weight of the block polymer surfactant. The composition according to any of claims 7 or 8, wherein the block polymer surfactant is an ABA-type alkoxylate block polymer comprising polyethylene oxide blocks ("A" block) and polypropylene oxide ( block "B") and wherein the alkoxylate block polymer is terminated at both ends with hydroxyl groups. The composition according to any one of claims 7 to 9, wherein the sum of the amounts of the water soluble solvent, the alkoxylate and the block polymer surfactant is at least 50% by weight of the composition. The composition according to any one of claims 1 to 10, comprising a nonionic cosurfactant selected from phenol alkoxylates. 12. The composition according to any of claim 11, comprising from 5 to 25% by weight of the non-ionic cosurfactant. The composition according to any one of claims 1 to 12, comprising less than 1% by weight of water. 14. A method for preparing the composition as defined in any one of claims 1 to 13, wherein the pesticide, the water soluble solvent, the inorganic thickener, the alkoxylate, optionally the block polymer surfactant and optionally the cosurfactant non-ionic contact. 15. A non-therapeutic method to control phytopathogenic fungi and / or unwanted plant growth and / or unwanted attack by insects or mites and / or to regulate plant growth, wherein the composition as defined in claims 1 to 13 it is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and / or the unwanted plants and / or the useful plants and / or their habitat.