EA045490B1 - SURFACTANT COMPOSITION AND ITS APPLICATION - Google Patents

Description

Field of technology to which the invention relates

The present invention relates to a surfactant composition. The surfactant composition, in particular, can be used as a low-foaming wetting agent for solid agrochemical preparations. The surfactant composition includes a sulfosuccinate-based compound and a C ₁₆ -C22 alkyl sulfate or an alkyl ether sulfate containing a C ₁₆ -C22 alkyl.

State of the art

An agrochemical formulation is usually a homogeneous and stable mixture of active ingredients and inert ingredients, making the final product easier, safer and more effective to apply to the target pest. The active ingredients used in agrochemicals can be prepared and delivered in different forms such as powders, granules, emulsions and dispersions. Accordingly, the agrochemical preparations may be in the form of a sprayable solid, sprayable liquid, sprayable granules, or the like.

One type of agrochemical may be a water-dispersible solid form that, once diluted, can be sprayed for agricultural use. In particular, such preparations include water-dispersible granules (WDG), dry bulk solids (DF) and wettable powders (WP) of a solid active ingredient or a liquid active ingredient applied to a solid carrier, which can give WDG, DF and WP preparations. For some active ingredients that are ultimately soluble in the final diluted system used for nebulization, pre-dispersion in water may be necessary to ensure dissolution. These specific examples of WDG may alternatively be described as water soluble granules (WSG).

Another type of agrochemical formulation is a stable suspension of the solid active ingredient(s) in a liquid, usually intended to be diluted with water before use. Such preparations typically include a suspension concentrate (SC) and a suspoemulsion (SE) preparation.

Another type of agrochemical formulation is one that delivers solid active ingredient(s) on inert or fertilizer carriers. Such preparations are usually prepared as granules for application to soil and are called slow-dispersing granule (GR) preparations.

In these preparations, the solid active ingredient or the liquid active ingredient applied to a solid carrier usually needs to be completely dispersed to the original particle size or left completely dispersed so that the drug then remains as a stable dispersion that is suitable for spraying. It is also desirable that the drug has good wetting ability. Surfactants are commonly added to agrochemical formulations to enhance the dispersion and wetting properties of the formulation and provide many other performance benefits.

One difficulty associated with agrochemical preparations that are based on active ingredients in solid dispersible form or pre-dispersed form is the development of foaming during dispersion and dilution. Foaming may occur when mixing preparations. This foaming may make it difficult to spray the spray liquid evenly. Other problems include overflow due to foaming or overflow of spray liquid over the top of the mixing vessel. In addition, foam formation may require the farmer to wait a long time for the foam to settle before spraying or may require the addition of foam control agents, which can be expensive, such as those based on silicone oil emulsion.

Surfactants in agrochemicals can be a major source of foaming. For example, alkyl sulfate and alkyl ether sulfate are known as wetting agents for agrochemicals. However, alkyl sulfate can cause significant foaming. International patent publication PCT No. 2014/172469 discloses the use of alkyl sulfate and alkyl ether sulfate in a blowing agent composition.

Various attempts have been made to produce low foaming agrochemicals WP and WDG. It has been discovered that alcohol alkoxylates can be used as low-foaming wetting agents. However, the resulting preparations have poor dispersion characteristics. To reduce foaming, salts of fatty acids are disclosed. However, the ability of fatty acid salts to reduce foaming is unsatisfactory.

It is necessary to provide a composition of surfactants having wetting properties that can reduce foaming in dispersions of agrochemicals such as WP and WDG. It is necessary to develop a method to reduce or eliminate foaming in dispersions of agrochemical preparations that are based on solid active ingredients. It is necessary to obtain a solid agrochemical preparation that has low foaming combined with good wetting ability.

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The essence of the invention

One aspect of the present invention is a surfactant composition that includes:

(a) a sulfosuccinate compound; and (b) a C ₁₆ -C ₂₂ alkyl sulfate or an alkyl ether sulfate containing a C ₁₆ -C ₂₂ alkyl.

Said surfactant composition is particularly a surfactant composition useful for a solid agrochemical composition.

Without being limited by theory, it is believed that the surfactant composition of the present invention provides a combination of reduced foaming and increased wetting ability. According to the invention, it has surprisingly been found that agrochemical preparations comprising a surfactant composition are characterized by reduced foaming during dispersion. Foaming of formulations can be easily measured using standard foaming tests known to one skilled in the art. In addition, the composition of surfactants can provide formulations with excellent wetting properties.

The term solid agrochemical composition as used in the present invention means an agrochemical preparation that contains a solid agricultural active ingredient itself or a solid/liquid agricultural active ingredient that is formulated in solid form. The solid agrochemical composition includes water-dispersible granules (WDG), dry bulk solids (DF), wettable powder (WP), suspension concentrate (SC), suspoemulsion (SE), slow-dispersing granules (GR) and water-soluble granules (WSG). ) and any other type of solid dispersible product as classified from time to time by Crop Life International organization. It should be understood that the solid agrochemical composition includes dispersing and/or diluting agrochemical preparations that are based on the solid active ingredient(s).

Another object of the present invention is a solid agrochemical composition comprising said surfactant composition and an agriculturally active ingredient. Accordingly, the solid agrochemical composition includes:

(a) an agriculturally active ingredient, in particular in solid form;

(b) a sulfosuccinate compound; and (c) a C ₁₆ -C ₂₂ alkyl sulfate or an alkyl ether sulfate containing a C ₁₆ -C ₂₂ alkyl.

In yet another aspect, the present invention relates to a method of reducing or eliminating foaming of a solid agrochemical composition, where the method includes the step of adding to the composition a surfactant composition comprising:

(a) a sulfosuccinate compound; and (b) a C16- _C22 alkyl sulfate or an alkyl ether sulfate containing a _C16 - _C22 alkyl.

Detailed Description of the Invention

In the present description, including the claims, the term including one or including is to be understood as synonymous with the term including at least one, unless otherwise indicated. The terms from and from ... to ... should be understood to include limit values.

A singular term means one or more than one (ie, at least one) entity.

It should be noted that when specifying any range of concentration, mass ratio or amount, any particular upper limit of concentration, mass ratio or quantity may be used in conjunction with any particular lower limit of concentration, mass ratio or quantity, respectively.

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

As used herein, the term alkenyl as a group or part of a group means an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be linear or branched. The group may contain multiple double bonds in a normal chain and the orientation around each is independently E or Z. Typical alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl. The group may be a terminal group or a bridging group.

As used in the present invention, the term hydroxyalkyl means an alkyl radical that is substituted with hydroxy groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxydecyl.

When used in the present invention, the term (C _n -C _m ) when applied to an organic group where n and m are both integers indicates that the group may contain from n carbon atoms to m carbon atoms.

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As used herein, the term agriculturally acceptable salts means salts derived from agriculturally acceptable non-toxic bases or acids, including inorganic or organic bases and inorganic or organic acids. Typical agriculturally acceptable salts provided in the present invention include an anion formed from the compound, for example, by deprotonation of a hydroxy group or hydroxyalkyl substituent, and one or more positively charged counterions. Suitable positively charged counterions include inorganic cations and organic cations, such as, for example, sodium cations, potassium cations, calcium cations, magnesium cations, isopropylamine cations, ammonium cations and tetraalkylammonium cations.

As used in the present invention, C ₁₆ -C ₂₂ alkyl sulfate means an alkyl sulfate that contains only C ₁₆ -C ₂₂ alkyl chain(s), or an alkyl sulfate that mainly contains C ₁₆ -C ₂₂ alkyl chains. An alkyl sulfate that primarily contains C ₁₆ -C ₂₂ alkyl chains is an alkyl sulfate that contains a mixture of C ₁₆ -C ₂₂ alkyl chain(s) as well as shorter alkyl chain(s) where the content is C ₁₆ -C ₂₂ -alkyl chain(s) is at least 90 wt.% based on all alkyl chains. As used herein, C ₁ -C ₁₄ alkyl sulfate means an alkyl sulfate that contains only C ₁ -C ₁₄ alkyl chain(s), or an alkyl sulfate that primarily contains C ₁ -C ₁₄ alkyl chains. An alkyl sulfate that primarily contains _C1 - _C14 alkyl chains is an alkyl sulfate that contains a mixture of € _1- € ₁₄ alkyl chain(s) as well as longer alkyl chain(s) where the content is _C1 - _C14 alkyl chain(s) is at least 90 wt.% based on all alkyl chains. This should be understood in the same sense when referring to the length of the alkyl chain in alkyl ether sulfates.

The surfactant composition of the present invention contains (a) a sulfosuccinate-based compound; and (b) a C ₁₆ -C ₂₂ alkyl sulfate or alkyl ether sulfate containing a C 16 -C 22 alkyl. Preferably, component (b) is a C16-C22 alkyl sulfate.

The sulfosuccinate compound includes agriculturally acceptable sulfosuccinic acid monoester salts, agriculturally acceptable sulfosuccinic acid diester salts, each of which may optionally be alkoxylated, as well as mixtures thereof.

Examples of sulfosuccinate-based compounds include, but are not limited to:

disodium monooctyl sulfosuccinate, disodium lauryl sulfosuccinate, disodium isodecyl sulfosuccinate, disodium tridecyl sulfosuccinate, diammonium lauryl sulfosuccinate, disodium laureth sulfosuccinate, disodium decyl-PEG-4-sulfosuccinate, disodium laureth-5-sulfosuccinate, disodium laurimide (MEA) sulfosuccinate, disodium cocoamide-MIPA-sulfosuccinate, disodium oleamido-MIPA sulfosuccinate, disodium oleylamido-PEO-2-sulfosuccinate, disodium cocamido-MEA sulfosuccinate, diammonium lauramido-MEA sulfosuccinate, sodium dioctyl sulfosuccinate, sodium bistridecyl sulfosuccinate, sodium dihexyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate.

Preferably, the sulfosuccinate-based compound is described by the general formula (I)

II o (I) where

Rs r ₄ -o-(-CH -CH ₂ -OCHR1 and R2, the same or different, mean ' where R ₃ means H, C1-C ₄ -alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl, such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl, preferably R ₃ is H or methyl;

R4 is C1- _C22 alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl, preferably C1-C16alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl, more preferably _C4 - _C16 alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl, even more preferably C8- _C16 - alkyl or hydroxyalkyl;

n is 0 or is an integer from 1 to 100, preferably 0 or is an integer from 1 to 50, more preferably 0 or is an integer from 1 to 30, preferably n is an integer from 1 to 30;

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X ⁺ means H or a cation, for example NH ₄ , an alkali metal such as sodium, potassium and calcium, an alkyl ammonium such as ethylamine, propylamine and isopropylamine and a hydroxyalkyl ammonium such as alkanolamine.

More preferably, the sulfosuccinate-based compound is represented by the general formula (I)

R2 O

II o (I) where R1 and R2, the same or different, mean R ₄ ---O---, where R4 means C1-C ₂₂ -alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl, preferably C ₁ -C ₁ 6-alkyl , alkenyl, hydroxyalkyl or hydroxyalkyl, more preferably C ₄ -C16-alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl, even more preferably C ₈ -C ₁₆ -alkyl or hydroxyalkyl;

X ⁺ means H or a cation, for example NH ₄ , an alkali metal such as sodium, potassium and calcium, an alkyl ammonium such as ethylamine, propylamine and isopropylamine and a hydroxyalkyl ammonium such as alkanolamine.

Other examples of sulfosuccinate-based compounds include Aerosol® series (Solvay), Agrilan® or Lankropol® series (Akzo Nobel), Empimin® series (Albright & Wilson), Cropol® series (Croda), Lutensit® series (BASF), Triton series ® (Union Carbide), Geropon® series (Solvay), Imbirol®, Madeol® or Polirol® series (Cesalpinia).

The C ₁₆ -C ₂₂ alkyl sulfate suitable for the present invention may be a linear alkyl sulfate or a branched alkyl sulfate. The C ₁₆ -C ₂₂ alkyl sulfate may be a primary alkyl sulfate or a secondary alkyl sulfate. In the case of branched alkyl sulfates, the C ₁₆ -C ₂₂ alkyl sulfate may include one, two or more branches. The C ₁₆ -C ₂₂ alkyl sulfate may be a mixture of alkyl sulfates having different alkyl chain lengths and may be a mixture of linear and branched alkyl sulfates.

C ₁₆ -C ₂₂ -Alkyl sulfate includes:

1) primary alkyl sulfates formed from alcohols obtained by oxosynthesis reaction from oligomers of propylene or n-butylene;

2) primary alkyl sulfates formed from lipids containing oleic acid;

3) primary alkyl sulfates, for example, the so-called tridecyl types, formed by the oligomerization of propylene over an acid catalyst followed by an oxosynthesis reaction;

4) primary alkyl sulfates formed from alcohols obtained using Neodol or Dobanol technology: they are products of the oxo-synthesis reaction of linear internal olefins or are products of the oxo-synthesis reaction of linear alpha-olefins. Olefins are produced by oligomerization of ethylene to form alpha-olefins, which are directly used or isomerized to internal olefins and metathesised to produce internal olefins of varying chain lengths;

5) primary alkyl sulfates formed using Neodol or Dobanol technology catalysts from internal olefins formed from raw materials that differ from those usually used to produce Neodol or Dobanol alcohols; internal olefins are obtained by dehydrogenation of petroleum paraffins;

6) primary alkyl sulfates formed by a conventional (for example, carried out at high pressure with cobalt catalysis) oxo-synthesis reaction from internal olefins; internal olefins are obtained by dehydrogenation of petroleum paraffins;

7) primary alkyl sulfates formed by a conventional (for example, carried out at high pressure with cobalt catalysis) oxo-synthesis reaction from alpha-olefins;

8) primary alkyl sulfates derived from natural linear fatty alcohols, such as those sold by Procter & Gamble Co.;

9) primary alkyl sulfates formed from Ziegler alcohols, such as those sold by Albermarle;

10) primary alkyl sulfates formed by the reaction of normal alcohols with Guerbet's catalyst (the purpose of this well-known catalyst is the dehydrogenation of two moles of a normal alcohol into the corresponding aldehyde, its aldol condensation and dehydration of the product, which is an alpha, beta-unsaturated aldehyde, which is then hydrogenated with producing a 2-alkyl branched primary alcohol, all in one reaction vessel);

11) primary alkyl sulfates formed by dimerization of isobutylene to form

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2,4,4'-trimethyl-1-pentene, which by oxosynthesis to produce an aldehyde, aldol dimerization, dehydration and reduction produces alcohols;

12) secondary alkyl sulfates formed by the addition of sulfuric acid to alpha or internal olefins;

13) primary alkyl sulfates formed by oxidation of paraffins using steps (a) oxidation of paraffin to form a fatty carboxylic acid; and (b) reducing the carboxylic acid to obtain the corresponding primary alcohol;

14) secondary alkyl sulfates formed by direct oxidation of paraffins to form secondary alcohols;

15) primary or secondary alkyl sulfates formed from various plasticizing alcohols, usually by the reaction of olefin oxo-synthesis, aldol condensation, dehydration and hydrogenation (examples of suitable oxo-synthesis catalysts are conventional Co or, more recently, Rh catalysts); And

16) primary or secondary alkyl sulfates, except linear primary ones, for example, phytol, farnesol, isolated from sources - natural products.

Preferably, the C ₁₆ -C ₂₂ alkyl sulfate is described by the general formula (II)

R ₅ OSO ₃ M ⁺ (II) where R ₅ means a C ₁₆ -C ₂₂ -alkyl or hydroxyalkyl group, linear or branched, M ⁺ means a cation such as sodium, potassium, magnesium, ammonium cation and their organic derivatives such as monoethanolamine, diethanolamine or triethanolamine. In some preferred embodiments, M ⁺ is sodium or ammonium.

Other examples of C ₁₆ -C ₂₂ alkyl sulfate include Lanette® E and Kolliphor® CSS (from BASF).

An alkyl ether sulfate containing C ₁₆ -C ₂₂ -alkyl can be described by the general formula (III)

R ₆ (AO) _n OSO ₃ M ⁺ (III) where R6 means a C ₁₆ -C ₂₂ alkyl or hydroxyalkyl group, linear or branched;

AO means ethylene oxide (EO), propylene oxide (PO) or a mixture thereof, preferably ethylene oxide;

n is the degree of alkoxylation, n may be an integer from 1 to 100, n is preferably an integer from 1 to 30, more preferably from 1 to 10;

M ⁺ means a cation such as sodium, potassium, magnesium, ammonium and their organic derivatives such as monoethanolamine, diethanolamine or triethanolamine. In some preferred embodiments, M ⁺ is sodium or ammonium.

Examples of the C ₁₆ -C ₂₂ alkyl containing alkyl ether sulfate include sodium cetostearyl ether sulfate, sodium cetyl ether sulfate, sodium stearyl ether sulfate such as the ALFOTERRA® series from Sasol.

In a preferred embodiment, said surfactant composition further comprises a C ₁ -C ₁₄ alkyl sulfate or an alkyl ether sulfate containing a C ₁ -C ₁₄ alkyl.

Accordingly, the present invention also relates to a surfactant composition that contains (a) a sulfosuccinate-based compound; (b) C ₁₆ -C ₂₂ -alkyl sulfate or alkyl ether sulfate containing C ₁₆ -C ₂₂ -alkyl; and (c) a C ₁ -C ₁₄ alkyl sulfate or an alkyl ether sulfate containing a C ₁ -C ₁₄ alkyl. Preferably, component (b) constitutes at least 5% by weight of (b) and (c), for example, from 5% by weight to 99% by weight of (b) and (c). More preferably, component (b) constitutes at least 8% by weight of (b) and (c), for example, from 8% by weight to 99% by weight of (b) and (c). Even more preferably, component (b) constitutes at least 10% by weight of (b) and (c), for example, from 10% by weight to 99% by weight of (b) and (c).

In some embodiments, said C ₁₆ -C ₂₂ alkyl sulfate or alkyl ether sulfate is branched. In some embodiments, said C ₁ -C ₁₄ alkyl sulfate or alkyl ether sulfate is branched. In some embodiments, both the C ₁₆ -C ₂₂ alkyl sulfate or alkyl ether sulfate component and the C ₁ -C ₁₄ alkyl sulfate or alkyl ether sulfate component are branched.

Examples of branched C ₁₆ -C ₂₂ alkyl sulfate include sodium heptadecyl sulfate, sodium isohexadecyl sulfate. Examples of the branched C ₁ -C ₁₄ alkyl sulfate include sodium isotridecyl sulfate, sodium isodecyl sulfate.

The surfactant composition may be formulated as a discrete composition for use in dispersing the active ingredient in solid form, for example formulated as WDG, SC or WP, or alternatively simply formulated together with the active ingredient.

The surfactant composition preferably contains the sulfosuccinate compound in an amount of 1% to 50%, more preferably 1% to 35%, based on the total weight of the surfactant composition.

The surfactant composition preferably contains a C ₁₆ -C ₂₂ alkyl sulfate or an alkyl ether sulfate containing a C ₁₆ -C ₂₂ alkyl in an amount ranging from 1% to 90%. In some

- In 5045490 embodiments, said amount is from 5% to 35%, based on the total weight of the surfactant composition. In some embodiments, the amount is from 70 to 90%, based on the total weight of the surfactant composition.

Another object of the present invention is a solid agrochemical composition comprising: (a) an agricultural active ingredient; (b) a sulfosuccinate-based compound; and (c) C16- _C22 -alkyl sulfate or alkyl ether sulfate containing _C16 - _C22 alkyl. In particular, a solid agrochemical composition has been prepared, comprising (a) an agriculturally active ingredient; (b) a sulfosuccinate-based compound; (c) C ₁₆ -C ₂₂ -alkyl sulfate or alkyl ether sulfate containing C ₁₆ -C ₂₂ -alkyl; and (d) a C ₁ -C ₁₄ alkyl sulfate or alkyl ether sulfate containing a C ₁ -C ₁₄ alkyl.

The agriculturally active ingredient is particularly an active ingredient in solid form, or the active ingredient itself is a solid, or the active ingredient is a solid or liquid that is formulated in a solid form, for example applied to a solid carrier.

An agriculturally active ingredient includes any chemical that adversely affects the lifespan, reproductive capacity and/or growth or metabolic function of plants, insects, fungi and/or various other types. In particular, the agriculturally active ingredient is one or more selected from the group consisting of a herbicide, an insecticide, a fungicide, an acaricide and a rodenticide.

The agriculturally active ingredient includes, but is not limited to, herbicides (for example, triazines, ureas and sulfonylureas), insecticides (for example, imidacloprid, fipronil and synthetic pyrethroids), fungicides, biocides, molluscicides, algaecides, plant growth regulators, anthelmintics, rodenticides, nematicides, acaricides , amoebicides, antiprotozoal substances, antidotes for agricultural plants, excipients or combinations thereof. Without limitation, examples of agricultural active ingredients in granular or powder form for use in agriculture include triazine herbicides such as simazine, atrazine, terbutylazine, terbutryn, promethrine and ametrine; urea herbicides such as diuron and fluometron; sulfonylurea herbicides such as chlorsulfuron, metsulfuron methyl, nicosulfuron and triasulfuron; sulfonanilide herbicides such as flumetsulam; organophosphorus insecticides such as azinphos methyl, chlorpyrifos, sulprophos and azametifos; carbamate insecticides such as aldicarb, bendiocarb, carbaryl and phenobucarb (2-sec-butylphenylmethylcarbamate); synthetic pyrethroids such as bifenthrin; fungicides including chlorothalonil, dimethomorph, benomyl, carbendazim, mancozeb; triazoles such as hexaconazole and diniconazole; and acaricides such as propargite.

In some embodiments, the agricultural active ingredient is a triazine, such as atrazine and simazine. In some embodiments, the agriculturally active ingredient is a triazine, urea, or a combination thereof in the WDG or WP formulation. It should be understood that the compositions may include one or more than one agriculturally active ingredient.

The solid agrochemical composition may include a surfactant composition that contains a sulfosuccinate compound and an alkyl sulfate/alkyl ether sulfate described in the present invention in an amount of 0.1% to 10%, preferably 0.5% to 5% % based on the total weight of the solid agrochemical composition.

The surfactant composition or agrochemical composition of the present invention may further include other agriculturally suitable ingredients/excipients such as solvents, pH modifiers, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, light protective agents, compatibilizers, antifoaming agents/antifoams, binding agents, neutralizing agents, corrosion inhibitors, dyes, odorants, flow enhancing agents, permeation aids, emollients, lubricants, tackifying agents, dispersants agents/dispersants, thickening agents, freezing point depressants, antimicrobials and insect repellents.

The surfactant composition or agrochemical composition may include an additional wetting agent. Additional wetting agents are preferably alkyl polysaccharides, alcohol ethoxylates and alkylphenol ethoxylates. Since many of them are in liquid form, they are often supplied in solid form by being incorporated into a solid matrix. Non-limiting examples of the alkyl polysaccharide class of wetting agents are alkyl polyglucosides prepared by reaction with glucose and a hydrocarbon-derived primary alcohol. Examples of additional wetting agent that can be used include APG® 325, PLANTAREN® 2000, PLANTARN® 1300, AGRIMUL® PG 2067 (all from Cognis Corporation), ATPLUS® 438 and ATPLUS® 452 (from Uniqema, Inc.). In some embodiments, the composition

- 6 045490 surfactants or agrochemical composition further includes an alkyl polysaccharide such as an alkyl polyglycoside (APG) as an additional wetting agent.

The surfactant composition or agrochemical composition may further include a fatty acid salt. A fatty acid salt suitable for the present invention may include any fatty acid suitable for use with an agricultural active ingredient. In one embodiment, the fatty acid salt is a C ₈ -C22 fatty acid salt, which may be saturated or unsaturated (eg, contain one or more multiple bonds, eg, cis and/or trans form). Without limitation, examples of saturated fatty acids include _C12 (lauric acid), Cu (myristic acid), _C16 (palmitic acid) and _C18 (stearic acid). Without limitation, examples of unsaturated fatty acids include C ₁₈ (oleic acid and elaidic acid). Fatty acid salts may include any suitable salts. Without limitation, examples of suitable salts include ammonium and alkylamine salts (eg, NH ₄ ⁺ , NHEt ₃ ⁺ ), alkali metal salts (eg, Li ⁺ , Na ⁺ , K ⁺ ) and alkaline earth metal salts (eg, Mg ²⁺ and Ca ^{2 +} ) and trivalent metal salts (for example, Al ³⁺ ). Without limitation, examples of suitable fatty acid salts include sodium stearate, sodium oleate, aluminum stearate, or combinations thereof.

The surfactant composition or agrochemical composition may further include antifoam agents. Suitable antifoams include all conventional antifoams, preferably silicone-based antifoams such as, for example, silicone oils. Preferred antifoaming agents are selected from the group of linear polydimethylsiloxanes having an average dynamic viscosity, measured at 25°C, ranging from 1000 to 8000 mPa -s, preferably from 1200 to 6000 mPa -s and containing silicon dioxide. Silica includes forms/modifications such as polysilicic acids, meta-silicic acid, ortho-silicic acid, silica gel, silicic acid gels, kieselguhr, precipitated SiO ₂ and the like. Antifoam agents from the group of linear polydimethylsiloxanes contain as their chemical backbone a compound of the formula HO-[Sj(CH ₃ ) ₂ -O-] _n -H, in which the end groups are modified, for example, by the formation of ethers or usually attached to -Sj groups (CH ₃ ) ₃ . The amount of silica can be varied over a wide range and is typically in the range of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.2% to 2% by weight of silica based on per weight of polydimethylsiloxane. Examples of this type of antifoam are Rhodorsil® Antifoam 416 and Rhodorsil® Antifoam 481 (Solvay). Other silicone antifoams include Rhodorsil® 1824 (Solvay), Antimussol® 4459-2 (Clariant), Antifoam V 4459 (Clariant), SE Visk and AS EM SE 39 (Wacker).

The surfactant composition or agrochemical composition may further include surfactants as dispersing agents, which include, but are not limited to, alkylphenol condensation salts, sulfonated lignin salts, polyacid resin copolymer salts, polyphenol formaldehyde resin salts, polyaryl sulfate salts. ethers such as tristyrylphenol ethoxylate sulfate salts, alkoxylated alkylphenols and alcohols, and block copolymers of ethylene oxide and propylene oxide. Examples of dispersant that can be used include Geropon® Ultrasperse, Geropon® T/36, Geropon® SC/213, Geropon® TA/72, all from Solvay, Atlox Metasperse 550S (Croda) and Tersperse® 2700 (Huntsman).

The surfactant composition or agrochemical composition may also include other insoluble materials that are used in agriculture, such as fillers and carriers, such as, but not limited to, natural and synthetic silicates and silicate minerals, inorganic oxides and hydroxides, and also natural and synthetically produced organic materials. Such materials can be added as porous carriers, as moisture-absorbing agents, to promote binding or agglomeration of the drug, and/or to adjust the weight of the drug to a suitable value. Examples of such fillers may include natural silicates such as diatomaceous earth, synthetic precipitated silica, clays such as kaolin, attapulgites and bentonites, also zeolites, titanium dioxide, iron oxides and hydroxides, aluminum oxides and hydroxides, amorphous and crystalline silica, diatomaceous earth, talc, mica, urea-formaldehyde and polyphenolic resins and calcium carbonate, ammonium sulfate, sodium tripolyphosphate, calcium phosphate, urea and sodium carbonate or organic materials such as bagasse, charcoal or synthetic organic polymers.

The solid agrochemical composition of the present invention may be WDG, DF, WP, SC, SE, GR, WSG or any other type of solid dispersant as classified by Crop Life International organization from time to time. For example, the solid agrochemical composition may be a suspension concentrate or suspoemulsion type preparation (SC, SE) comprising water.

The solid agrochemical composition is usually dispersed in an aqueous medium before use. Dispersion can be carried out using any suitable techniques. For example, a technique can

- 7 045490 take into account the nature of the composition and compatibility with the components of the composition. In a preferred embodiment, dispersion of the composition in an aqueous solution is carried out either manually or with minimal mechanical stirring. Mechanical mixing may include stirring, mixing, combining, and other suitable techniques. The pH value of the aqueous dispersion may be from 2.0 to 10.0, preferably from 5.0 to 9.0.

The solid agrochemical composition can be prepared by mixing a combination of components, including the surfactant composition described in the present invention. Combination of components may mean a homogeneous mixture of components, optionally formulated together as WDG, DF, WP, SC, SE, GR or WSG, or simply placing the respective components together in a vessel for dispersing or mixing, or any other degree of mixing them together. Preparation of an aqueous dispersion of a solid agrochemical composition means using and dispersing the combination, this may involve preparing all components prepared together as WDG, DF, WP, SC, SE, GR or WSG, or preparing the active ingredient together as WDG, DF, WP , SC, SE, G or WSG and the surfactant composition or part of the surfactant composition described in the present invention is provided as separate components or as a tank mixture in a tank or dispersion vessel. If at least one or more components are provided separately, they may optionally be mixed first prior to dispersion or, alternatively, simply mixed during the dispersion procedure.

Another aspect of the present invention is a method for reducing or eliminating foaming of a solid agrochemical composition, comprising the step of adding surfactants described in the present invention to the agrochemical composition. Foaming in a dispersion of an agrochemical composition can be reduced by including said surfactant composition in the agrochemical composition.

The solid agrochemical compositions of the present invention are particularly suitable for use in crop protection where the compositions are applied to plants, plant parts or a growing area, for example, the soil of a growing area.

Examples

Materials.

Atrazine: 97% purity, Hebei Shanli Chemical Co., Ltd;

chlorothalonil: from Suli Co., Ltd.;

simazine: Zhejiang Zhongshan Chemical Industry Group Co., Ltd.;

sulfosuccinate (SS) compound: sodium dioctyl sulfosuccinate;

alkyl sulfate (AS):

AS1: C ₁₆ -C ₁₈ -sodium alkyl sulfate, synthesized from natural C16-C18 alcohol, C ₁₆ /C 18 = 29/71;

AS2: C ₁₂ -C ₁₄ -sodium alkyl sulfate;

alkyl polysaccharide (AP): APG0810 from Yangzhou Chenhua New Material Co., Ltd.;

dispersants: Geropon® Ultrasperse from Solvay;

Water C: CIPAC standard water, hardness 500 ppm;

water D: CIPAC standard water, hardness 342 ppm.

Study of drugs obtained using the method of mixing liquids.

The ability of the surfactant composition of the present invention to reduce foaming was tested using formulations prepared by mixing the active ingredient, dispersant and wetting agent in water without granulation (liquid mixing technique). This test provides a rapid and accurate determination of foaming and its results are in good agreement with those obtained using the standard foaming test developed by the Collaborative International Pesticides Analytical Council (CIPAC) and described in Method MT 47.2, which uses a granulation procedure.

First, the foaming of the preparations that were obtained using the above liquid mixing procedure was examined in comparison with the foaming of granular preparations, which was studied according to the method described by CIPAC Method MT 47.2. The results are shown in the table below. 1.

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Table 1

#1 #2 #3 #4 A drug Active ingredient Atrazine Dispersant means Geropon® Ultrasperse Wetting agent Rodapon® LS-94/WP Geropon®L-WET/P Methodology preparations Granulated tion Mixing liquids Granulated tion Mixing liquids Foaming (mm) 0" 82 78 76 62 G 82 78 16 10 3' 54 78 2 6

Rodapon® LS-94/WP used in the above studies was a wetting agent that itself caused high foaming, while Geropon® L-WET/P was a wetting agent that caused comparatively low foaming. The results show that the data for the foaming of drugs obtained using the liquid mixing method are characterized by patterns that are generally similar to the data for drugs obtained using the standard granulation method, for high and low foaming drugs. These results indicate that liquid mixing techniques can provide an accurate assessment of foaming in agrochemical formulations.

To study foaming, atrazine preparations were prepared using the method of mixing liquids and the composition given below:

table 2

Components Content (wt.%; excluding filler) Atrazine (97%) 92.8% Dispersant 4.5% Surfactant composition 2%

The drugs were obtained according to the following methods. The active ingredient atrazine was jet milled before use and then mixed with a dispersant to form a powder mixture. The powder mixture was then diluted with Water D (CIPAC standard water, hardness 342 ppm) to form 5 wt.% (solids content) solution A. Solution B was prepared by diluting the surfactant composition with water D to obtain the final solids content, equal to 2.5 wt.%. Freshly prepared solutions A and B were mixed in a cylinder to evaluate the foam. Typically, 19.46 g of solution A and 0.8 g of solution B were added to the cylinder, then filled to 200 ml with water D. The cylinder was then inverted 30 times. Then the cylinder was placed vertically and kept in a water bath at 30°C. At different times after mixing, i.e. after 0 s, 1 min and 3 min, the volume of foam formed in the preparations was measured and recorded.

Various compositions of surfactants were studied and the results of the foaming study are given below in table. 3.

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Table 3

Composition of surfactants (wt.%) Foam volume (mm) # SS AS1 AS2 AR AR 0 G 3' EX1 10.0 90.0 - - 38 thirty thirty EX2 15.0 85.0 - - 40 8 0 EX3 30.0 70.0 - - 48 16 4 EX4 50.0 50.0 - - 46 8 2 EX5 70.0 30.0 - - 52 26 6 EX6 5.0 5.0 90.0 - 56 56 40 EX7 5.0 10.0 85.0 - 80 22 10 EX8 15.0 15.0 70.0 - 72 28 16 CE1 - 100 - - 50 50 50 SE2 100 - - - 80 80 80 SEZ 10 - 90 - 86 86 86 CE4 15 - 85 - 88 88 88 CE5 20 - 80 - 86 86 86 CE6 - - 100 - 78 78 78 CE7 25 - 55 20 72 72 72

EX means example and CE means comparative example.

The results show that the surfactant compositions of the present invention result in markedly reduced foaming compared to other surfactant compositions tested. Reduced foaming was indicated by a reduced volume of foaming in the preparations after mixing.

Study of WDG drugs.

In this set of experiments, WDG formulations were prepared and formulation characteristics, including suspendability, foaming, and disintegration, were examined.

WDG granules were obtained having the compositions indicated in the table below. 4.

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Table 4

EX9 EX10 CE8 CE9 EHP SEE YOU EX12 SEP Drug (wt.%) Atrazine (97%) 92.8 92.8 92.8 92.8 - - - - Chlorothalonil - - - - 91.5 91.5 - - Simazine - - - - - - 92.8 92.8 Wetting agent 1 2 2 - - 2 - 2 - Wetting agent 2 - - 2 2 - 2 - 2 Dispersant means 4.5 4.5 4.5 4.5 6 6 4 4 Kaolin 0.7 0.2 0.7 0.2 0.5 0.5 1.2 1.2 EDTA-2Na - 0.5 - 0.5 - - - - Total 100 100 100 100 100 100 100 100

Wetting agent 1 is a surfactant composition corresponding to Example 4. Wetting agent 2 is a surfactant composition corresponding to Comparative Example 6.

Granular preparations were prepared by first grinding the solid active ingredient and then mixing with a dispersant and a powdered wetting agent in a laboratory mixer. Approximately 20% (w/w) water was added and the powder was mixed with shaking. The slightly wet powder was then extruded through a 1mm laboratory scale sieve in a basket extruder. The extruded filaments were divided into approximately equal lengths by shaking and then dried to a residual water content of approximately 0.5% (w/w).

Foaming of the drugs was studied according to the method described above. Foaming at room temperature and 30°C (1 min after stirring) was determined respectively.

Suspensibility of the formulations was determined using the procedure described in CIPAC Method MT 15. Typically, the granules (2.5 g) were dissolved in water C (CIPAC standard water, hardness 500 ppm) at 30°C and then transferred to a cylinder. The sample was filled to 250 ml with water C and the cylinder was sealed. The sample was sufficiently mixed and then placed in a water bath at 30°C for 30 minutes. Then 225 ml of the suspension was taken from the top and the remaining 25 ml at the bottom was transferred to a glass plate, dried and weighed. The degree of suspension was calculated using the formula: (total mass of granules - mass of residue)/(total mass of granules). In this case, the total mass of the granules was 2.5 g.

Loosening was determined using the following method. 100 ml of water C (30°C or 10°C) was added to the cylinder, and 1.0 g of WDG granules was transferred into the cylinder and sealed. The cylinder was turned at a rate of 1 turn every 2 s until the granules were completely dispersed. The time until complete dispersion was obtained was recorded. The results are shown in the table below. 5.

Table 5

EX9 EX10 CE8 CE9 EX1 1 SEE YOU EX12 SEP Suspensibility 98.2% 98.6% >99% 99% 95% >99% 98.1% 98.2% Foaming (30°C, mm) 0 0 76 80 0 70 8 68 Loosening (30°C) 28" 28" thirty" thirty" thirty" 32" thirty" 36" Loosening (10°C) 52" 48" >120” 60" 52" 70" 56" >120”

The results show that the surfactant composition of the present invention (eg, wetting agent 1) resulted in satisfactory suspension

Claims (14)

sti. In addition, formulations containing the surfactant composition of the present invention exhibit reduced foaming compared to those containing only the short chain alkyl sulfate (eg, wetting agent 2). In addition, preparations containing the surfactant composition of the present invention are characterized by reduced disintegration time at low temperature. This rapid disintegration is particularly advantageous for solid agrochemicals, especially when used in low temperature environments. CLAIM 1. Solid agrochemical composition containing an agriculturally active ingredient and a composition of surfactants: (a) a sulfosuccinate compound; and (b) a C ₁₆ -C ₂₂ alkyl sulfate or an alkyl ether sulfate containing a C ₁₆ -C ₂₂ alkyl. 2. The solid agrochemical composition of claim 1, wherein the sulfosuccinate compound is an agriculturally acceptable sulfosuccinic acid monoester salt, an agriculturally acceptable sulfosuccinic acid diester salt, or a mixture thereof. 3. Solid agrochemical composition according to claim 1 or 2, where the sulfosuccinate-based compound is described by the general formula (I) II o (I) where _{R 0} D CH oR1 and R2, the same or different, mean ' where R ₃ means H, C1-C ₄ -alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl; R ₄ is C1- _C22 alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl; n is 0 or an integer between 1 and 100; X ⁺ means H or cation. 4. Solid agrochemical composition according to claim 3, where in the general formula (I) R1 and R2, the same or different, mean R ₄ ---O--; R4 is C1- _C22 alkyl, alkenyl, hydroxyalkyl or hydroxyalkyl; X ⁺ means H or cation. 5. Solid agrochemical composition according to any one of claims 1-4, where C16- _C22 alkyl sulfate is described by the general formula (II) R ₅ OSO3 ^- M ⁺ (II), where R ₅ means a C ₁₆ -C ₂₂ alkyl or hydroxyalkyl group, linear or branched; M ⁺ means cation. 6. Solid agrochemical composition according to any one of claims 1-4, where the alkyl ether sulfate containing C ₁₆ -C ₂₂ -alkyl is described by the general formula (III) R ₆ (AO) _n OSO ₃ ^- M ⁺ (III), where R6 means a C ₁₆ -C ₂₂ alkyl or hydroxyalkyl group, linear or branched; AO means ethylene oxide (EO), propylene oxide (PO) or a mixture thereof; n denotes the degree of alkoxylation and is an integer ranging from 1 to 100; M ⁺ means cation. 7. Solid agrochemical composition according to any one of claims 1 to 6, where the composition of surfactants further includes: (c) C ₁ -C ₁₄ -alkyl sulfate or alkyl ether sulfate containing C ₁ -C ₁₄ -alkyl. 8. Solid agrochemical composition according to claim 7, where component (b) is at least 5 wt.% of the total weight of components (b) and (c). 9. Solid agrochemical composition according to any one of claims 1 to 8, wherein the sulfosuccinate-based compound is contained in an amount equal to from 1 to 50% based on the total weight of the surfactant composition. - 12 045490 10. Solid agrochemical composition according to any one of claims 1 to 9, where C16- _C22 alkyl sulfate or alkyl ether sulfate containing C^-Cr alkyl is contained in an amount equal to from 1 to 90% based on the total weight of the composition surfactants. 11. Solid agrochemical composition according to any one of claims 1 to 10, wherein the agriculturally active ingredient is one or more substances selected from the group consisting of a herbicide, an insecticide, a fungicide, an acaricide and a rodenticide. 12. Solid agrochemical composition according to any one of claims 1 or 11, where the solid agrochemical composition contains the specified composition of surfactants in an amount equal to from 0.1 to 10% based on the total weight of the solid agrochemical composition. 13. Solid agrochemical composition according to any one of claims 1 to 12, where the solid agrochemical composition is water-dispersible granules (WDG), dry bulk substance (DF), wettable powder (WP), suspension concentrate (SC), suspoemulsion (SE ), slow dispersing granules (GR) or water soluble granules (WSG). 14. A method for reducing or eliminating foaming of a solid agrochemical composition according to claim 1, comprising the step of adding to the agrochemical composition of the active substance a surfactant composition containing: (a) a sulfosuccinate-based compound and (b) Ci ₆ -C ₂₂ alkyl sulfate or sulfate alkyl ether containing C1 ₆ -C ₂₂ -alkyl. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky lane, 2 -