Surfactant combination

Abstract

This invention relates to a surfactant composition comprising: a) an anionic component A (hereinafter referred to as surfactant component A), which is selected from C 10 -C 14 Sodium alkylbenzene sulfonate, such as linear dodecylbenzene sulfonate; and b) non-anionic component B (hereinafter referred to as surfactant component B), which is selected from compounds having formula (I) and mixtures thereof, R-O-(CH2CH2-O). n -H(I), where R is a branched C8-C 10 Alkyl, particularly 2-ethylhexyl or 2-propylheptyl, and n is an integer in the range of 0 to 10, particularly in the range of 0 to 6.

Description

[0001] This invention relates to a surfactant composition comprising an anionic component A and a nonionic surfactant component B, wherein the anionic component A is selected from C. 10 -C 14 Alkylbenzene sulfonates.

[0002] Agricultural chemically active compounds (such as herbicides, fungicides, insecticides, safeners, etc.) as well as adjuvants for pest control are typically applied as aqueous diluents to sites where pests are to be controlled.

[0003] For ease of handling and application safety, agrochemically active compounds and adjuvants for pest control are typically marketed as agrochemical formulations containing one or more agrochemically active compounds and / or adjuvants. Examples of agrochemical formulations that can be diluted with water include liquid formulations such as emulsifiable concentrates (EC), oil dispersions (OD), aqueous emulsions (EW), fine emulsions (ME), suspensions (SE), aqueous suspension concentrates (SC), capsule suspensions (CS), and soluble liquids (SL), as well as solid formulations such as dispersible granules (DG), wettable granules (WG), dispersible powders (DP), and wettable powders (WP). These formulations must be designed in a way that allows for easy dilution with water to the desired application concentration and ensures uniform distribution of the active ingredient in the aqueous application form. When diluted with water, the formulation must also not cause severe foaming or emulsification. In addition, aqueous diluents should be kept stable to prevent sedimentation or emulsification of agricultural active compounds, thereby avoiding clogging of spraying equipment and inaccurate dosage of agricultural chemical active compounds.

[0004] Surfactants (hereinafter also referred to as surfactants) play a crucial role in agrochemical formulations. On the one hand, they must ensure the rapid and uniform distribution of the components of agrochemical formulations in aqueous application forms, especially if the components are not readily miscible with water. On the other hand, surfactants are needed in liquid multiphase formulations (such as SC, OD, EW, SE, and ME formulations) to stabilize these phases, thereby preventing the aggregation, agglomeration, or condensation of the dispersed phase, and, in the case of OD and SC formulations, also preventing particle size growth of the dispersed solid phase. In some cases, surfactants even act as adjuvants, i.e., they enhance the activity of the corresponding biocidal compounds.

[0005] Surfactants used in agrochemical formulations can be anionic, nonionic, or cationic. They can be polymeric, meaning they have a molecular weight (number average) of 600 g / mol or higher, for example, up to 10,000 g / mol, or nonpolymeric, meaning they have a molecular weight (number average) of less than 600 g / mol, for example, in the range of 200 to < 600.

[0006] As is well known, surfactants function by reducing surface tension. For this purpose, surfactants must tend to migrate to the interface rather than remain in the solution within the bulk liquid phase. To achieve this, they must possess both hydrophilic and lipophilic groups. Conversely, excessively high solubility in either phase will impair their effectiveness. Furthermore, surfactants must be able to form a coagulated film at the interface, either alone or in combination with other surfactants, thereby stabilizing the dispersed phase and preventing aggregation, agglomeration, or coagulation. In addition, surfactants must migrate to and adsorb onto the interface rapidly enough to ensure sufficient reduction of interfacial tension during emulsion formation.

[0007] Often, combinations of one or more anionic surfactants and one or more nonionic surfactants are used in agrochemical formulations to achieve desired stability and dilution properties.

[0008] As is evident from the above, the molecular structure and molecular weight of a surfactant typically determine its suitability for a particular type of formulation. Various concepts have been established that allow for some prediction of whether a particular surfactant is suitable for a specific type of formulation, most notably Griffin's hydrophilic-lipophilic balance (HLB) concept. However, the correlation between chemical structure and its emulsifying activity is complex and difficult to predict, especially in the case of surfactant combinations.

[0009] Calcium alkylbenzene sulfonates, the calcium salts of alkylbenzene sulfonic acids (such as calcium dodecylbenzene sulfonate, hereinafter referred to as CDBS or CaDBS), are widely used surfactants for stabilizing oil-in-water emulsions (o / w emulsions). Due to the hydrophobic nature of these substances, CaDBS, for example, has an HLB value of approximately 7, they are soluble in the oil phase of the aforementioned formulations. Furthermore, calcium salts of alkylbenzene sulfonic acids are known to provide low interfacial tension, and they readily accumulate on the surface of the formed oil droplets when the formulation is diluted with water. This promotes the spontaneous emulsification and stabilization of the resulting emulsion. Therefore, calcium salts of alkylbenzene sulfonic acids are frequently used as surfactants in agrochemical formulations containing oil components, i.e., in emulsifiable concentrates (ECs), aqueous emulsions (EWs), microemulsions (MEs), and oil dispersions (ODs). Because CaDBS is a solid, it is typically supplied in liquid formulations in organic solvents for ease of handling.

[0010] For example, US 2004 / 0063583 discloses an emulsifiable concentrate of a pyrethroid insecticide containing a hydrophilic nonionic surfactant of the group consisting of calcium dodecyl sulfonate, polyoxyethylene polyaryl ether and polyoxyethylene-co-polyoxypropylene polyaryl ether, a benzyl ester solvent (such as benzyl acetate), and a hydrocarbon solvent.

[0011] WO 2007 / 095163 discloses an emulsifier system comprising 25% to 80% by weight of a hydrophobic anionic surfactant (such as calcium dodecylbenzenesulfonate) and 20% to 75% by weight of a hydrophilic surfactant having an HLB in the range of 11-18.

[0012] One drawback of using calcium salts of alkylbenzene sulfonic acids (such as CaDBS) to stabilize aqueous emulsions is the sensitivity of the emulsions to high salinity and alkalinity conditions. Under these conditions, the emulsion may become unstable and oil droplet coalescence may occur. Therefore, these surfactants are unsuitable for stabilizing aqueous emulsions under high salinity or alkalinity conditions, particularly in aqueous phases with high concentrations of alkali metal ions, which may occur when the formulation contains inorganic buffer salts and / or anionic biocidal compounds, or when the formulation is mixed with said buffer salts or anionic biocidal compounds. Furthermore, calcium salts of alkylbenzene sulfonic acids are not particularly suitable for stabilizing multiphase formulations containing dispersed solids, especially aqueous multiphase formulations such as SC and SE formulations.

[0013] Therefore, the object of the present invention is to provide surfactants that exhibit properties similar to CaDBS in the spontaneous emulsification of oil-containing agricultural chemical formulations to form aqueous emulsions and in stabilizing aqueous emulsions. Furthermore, these surfactants should have low sensitivity to saline or alkaline conditions. Additionally, these surfactants should be able to stabilize formulations containing dispersed solids (such as SC formulations and suspensions) that cannot be sufficiently stabilized by calcium salts of alkylbenzene sulfonic acids.

[0014] Surprisingly, the surfactant combinations disclosed herein meet the above requirements. These surfactant combinations comprise an anionic component A (hereinafter referred to as surfactant component A) and a nonionic component B, wherein the anionic component A is selected from C. 10 -C 14 Sodium alkylbenzene sulfonate, wherein the nonionic component B is selected from branched alkanols, branched alkanol ethoxylates and mixtures thereof having the formula (I) disclosed herein.

[0015] Therefore, the present invention relates to surfactant combinations as disclosed herein, comprising

[0016] a) Anionic component A (hereinafter referred to as surfactant component A), which is selected from C10 -C 14 Sodium alkylbenzene sulfonate, especially those selected from C 11 -C 13 Sodium alkylbenzene sulfonate, and particularly selected from sodium dodecylbenzene sulfonate, and

[0017] b) Nonionic component B (hereinafter referred to as surfactant component B), which is selected from compounds having formula (I) and mixtures thereof.

[0018] RO-(CH2CH2-O) n -H(I)

[0019] in

[0020] R is the branch C8-C. 10 Alkyl groups, particularly 2-ethylhexyl or 2-propylheptyl; and

[0021] n is an integer in the range of 0 to 10, and more specifically in the range of 0 to 6.

[0022] The surfactant compositions of this invention are associated with several benefits. In particular, they exhibit similar or even better emulsifying properties compared to their corresponding calcium alkylbenzene sulfonate counterparts, while showing lower sensitivity to saline or alkaline conditions frequently encountered in or during the application of agrochemical formulations. Specifically, they possess high solubility, exceeding that of the corresponding C... 10 -C 14 Sodium alkylbenzene sulfonate and component (B) are expected to have the known solubility when used alone. Furthermore, they are compatible with the corresponding C. 10 -C 14 Sodium alkylbenzene sulfonate promotes the self-emulsification of water-immiscible liquids better than calcium alkylbenzene sulfonate. Compared to calcium alkylbenzene sulfonate, the surfactant combination of the present invention provides increased stability of solid organic particles in aqueous suspensions relative to aggregation, sedimentation, and particle growth. Furthermore, the combination of components A and B has better stability than the individual corresponding components C. 10 -C 14 Sodium alkylbenzene sulfonate and its corresponding C 10 -C 14 Calcium alkylbenzene sulfonate has a lower Krafft temperature. Therefore, aqueous emulsions and suspensions containing the surfactant combination of the present invention are less sensitive to low temperatures. Furthermore, compared to the corresponding C... 10 -C 14 Sodium alkylbenzene sulfonate and its corresponding C 10 -C 14 Compared to calcium alkylbenzene sulfonate, the surfactant combination of the present invention exhibits reduced foaming during emulsification.

[0023] As a result, the surfactant combinations of the present invention are particularly useful not only for stabilizing aqueous emulsions but also for stabilizing aqueous suspensions. Due to their properties, they are particularly useful as surfactants in agrochemical formulations. Therefore, the present invention also relates to the following aspects:

[0024] • The use of surfactant combinations as surfactants in agrochemical formulations, as described herein;

[0025] • The surfactant combinations described herein are used for stabilizing aqueous diluents of agricultural chemical formulations and / or for promoting the dilution of agricultural chemical formulations in water.

[0026] • The use of surfactant combinations as described herein for stabilizing multiphase formulations of aqueous agrochemicals.

[0027] In another aspect, the present invention relates to agricultural chemical formulations, and more particularly to liquid agricultural chemical formulations, comprising...

[0028] i. As disclosed herein, and

[0029] ii. At least one agricultural chemical compound, selected from biohazard-killing compounds, biohazard-killing safeners, and mixtures thereof.

[0030] In another aspect, the present invention relates to an aqueous spray liquid containing...

[0031] i. Surfactant combinations as disclosed herein;

[0032] ii. At least one agricultural chemical compound, selected from biohazard-killing compounds, biohazard-killing safeners, and mixtures thereof;

[0033] iii. Water.

[0034] In this context and hereinafter, the term "immiscible with water" should be understood as a corresponding water-immiscible compound having a solubility in deionized water of less than 10 g / L, particularly less than 5 g / L or less than 1 g / L, at 20°C and 1 bar. Similarly, the term "water-insoluble" should be understood as a corresponding water-insoluble compound having a solubility in deionized water of less than 10 g / L, particularly less than 5 g / L or less than 1 g / L, at 20°C and 1 bar.

[0035] In this context and below, the term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. In the context of alkyl, the term C... k -C m Alkyl groups refer to the group of alkyl groups having k to m carbon atoms, i.e., having the formula C p H2 p+1Alkyl groups, where p is an integer spanning the range specified by integers k and m.

[0036] According to the present invention, compounds having formula (I) comprise a branched aliphatic group R, which is selected from branched alkyl groups having 8 to 10 carbon atoms. In preferred branched alkyl groups, the oxygen atom bonded to R is bonded to a CH2 group. In particular, the branched alkyl group R is selected from those having O-(CH2CH2-O). n Those branches at the carbon atom adjacent to the CH2 group of the -H moiety. Examples of R include, but are not limited to, 6-methylheptyl, 2-methylheptyl, 2-ethylhexyl, 2,2-dimethylhexyl, 2,2,4-dimethylpentyl, 7-methyloctyl, 2-methyloctyl, 2-methyldecyl, and 2-propylheptyl. In particular, R is 2-ethylhexyl or 2-propylheptyl.

[0037] Component B may be a single compound having formula (I) or a mixture of compounds having formula (I). In particular, component B is a mixture of compounds having formula (I). In these mixtures, the compounds having formula (I) preferably have the same group R, but differ from each other in the value of n.

[0038] Specifically, component B comprises at least 5% by weight, and particularly at least 10% by weight, of a compound having formula (I) in which n is 0, based on the total weight of component B.

[0039] Preferably, component B comprises at least 5% by weight, particularly at least 10% by weight, of a compound having formula (I) wherein n is 0, based on the total weight of component B. Preferably, the total amount of the compound having formula (I) wherein n is 0 does not exceed 70% by weight, particularly 50% by weight, and especially 40% by weight, based on the total weight of component B.

[0040] Specifically, component B is a mixture of compounds having formula (I), comprising a compound having formula (I) wherein n is 0 (hereinafter referred to as compound I0) and at least one other compound having formula (I) wherein n is in the range of 1 to 10, particularly in the range of 1 to 6 (hereinafter referred to as compound I). n≠0 Preferably, component B is compound I0 comprising, in each case, 5% to 70%, particularly 10% to 50%, particularly 10% to 30% by weight, based on the total weight of component B, and one or more compounds I0 comprising, in each case, 30% to 95%, particularly 50% to 90%, particularly 60% to 90% by weight, based on the total weight of component B. n≠0 A mixture.

[0041] The composition of the present invention further contains an anionic component A, which is selected from C 10 -C 14 Sodium alkylbenzene sulfonate, especially C 11 -C 13 Sodium alkylbenzene sulfonate, and especially sodium dodecylbenzene sulfonate. C 10 -C 14 Alkyl groups can be straight-chain or branched, and are preferably straight-chain C12 groups. 10 -C 14 Alkyl groups, especially straight-chain C 11 -C 13 Alkyl groups, especially straight-chain C 12 Alkyl group. In C 10 -C 14 In the context of alkylbenzene sulfonates, the straight-chain C 10 -C 14 Alkyl groups can be described by formula R'

[0042] CH(R a (R) b )(R')

[0043] Where R a It is (CH2) o H, and R b It is (CH2) p CH3

[0044] Where o is an integer in the range of 0 to 12, particularly in the range of 0 to 10, and p is an integer in the range of 1 to 13, and where o+p is in the range of 9 to 13, particularly in the range of 10 to 12, and especially in the range of 11.

[0045] C 10 -C 14 C of sodium alkylbenzene sulfonate 10 -C 14 The alkyl group is preferably positioned para-positioned on the benzene ring relative to the sulfonate group. Therefore, a particularly preferred C... 10 -C 14 Sodium alkylbenzene sulfonate can be described by the following formula A'

[0046]

[0047] Where R a and R b As defined above, where o+p is in the range of 10 to 12, and especially 12.

[0048] In the surfactant composition of the present invention, the weight ratio of anionic component A to non-anionic component B is typically in the range of 10:1 to 1:10, particularly in the range of 5:1 to 1:2, and particularly in the range of 4:1 to 1:1.

[0049] Preferably, as determined by DIN EN 13955:2003-03, the combination of components A and B has a low clave characteristic at temperatures close to 0°C (e.g., in the range of 0°C to 5°C). A clave characteristic is a narrow temperature range above which a turbid surfactant solution will become clear.

[0050] The surfactant assemblies of the present invention are particularly effective in emulsifying large quantities of water-immiscible liquids, especially solvents (such as hydrocarbons, vegetable oils and mixtures thereof), by the fact that they form Winsor IV type microemulsions in a 1:1 water / decane mixture after homogenization at 20°C.

[0051] PA Winsor, Trans. Farady Soc. [Faraday Society Journal] 44 (1948) 376-398 proposes classifying liquid formulations containing oil, water, and surfactants into four categories, namely Winsor systems I-IV (see also M. Hloucha, Ullmann's Encyclopedia of Industrial Chemistry 2015, "Microemulsions" - https: / / doi.org / 10.1002 / 14356007). A prerequisite for this classification is that the formulation is in equilibrium, meaning the macroemulsion has separated into layers. Winsor type I systems consist of two separate phases: an oil phase and an aqueous phase containing dissolved surfactants. Winsor type II systems consist of an oil phase with dissolved surfactants and an aqueous phase. Winsor type III systems consist of three phases: i) an intermediate phase containing oil, surfactants, and water; ii) an excess of water; and iii) an excess of oil. The Winsor IV system consists of one phase of oil, water, and surfactant.

[0052] The surfactant combinations of the present invention can be combined with one or more additional nonionic surfactants having an HLB of at least 12 according to Griffin, for example in the range of 12 to 18, particularly in the range of 13 to 18 or 14 to 18. These combinations are particularly suitable for the production of stable aqueous emulsions, microemulsions or nanoemulsions containing a variety of organic and water-immiscible solvents and biocidal compounds.

[0053] If present, the total amount of additional nonionic surfactants is in a weight ratio of 1:10 to 10:1 to the surfactant combination of the present invention, particularly in a range of 1:5 to 5:1.

[0054] Suitable nonionic surfactants according to Griffin, with an HLB of at least 12, for example in the range of 12 to 18, particularly in the range of 13 to 18 and especially in the range of 14 to 18, include C with an ethoxylation degree of at least 20, for example in the range of 20 to 50. 10 -C 20 Ethoxylated sorbitol monoesters of fatty acids, C8-C 10 -Alkyl polyglucoside, ethoxylated C8-C with a degree of ethoxylation of 11 to 50 20 Alkyl alcohols, ethoxylated vegetable oils with an ethoxylation degree of at least 20, for example, in the range of 20 to 50, and ethoxylated C4-C16-alkylphenols with an ethoxylation degree in the range of 11 to 50. Particularly preferred are ethoxylated C8-C16 alkylphenols with an ethoxylation degree of 11 to 50. 20 Alkane alcohols, ethoxylated vegetable oils with an ethoxylation degree of at least 20, for example, in the range of 20 to 50, wherein the latter is even more preferred.

[0055] A particularly preferred group of nonionic surfactants according to Griffin, having an HLB of at least 12, for example, in the range of 12 to 18, particularly in the range of 13 to 18 and especially in the range of 14 to 18, is ethoxylated vegetable oils with a degree of ethoxylation of at least 20, for example, in the range of 20 to 50, particularly selected from the group consisting of ethoxylated castor oil and ethoxylated soybean oil. These surfactants are commercially available under the following brands: Agnique CSO-16 to CSO-40, Agnique SBO 30, Emulpon CO-360, Ethox CO-16, Berol 904, Alkamuls OR 36, DEHSCOFIX CO 70, DEHSCOFIX CO 105, ENVIOMET EM 1036, ENVIOMET EM 1054, TOXIMUL 8242, TERGITOL ECO-36, and NOVEL EL-40.

[0056] As previously mentioned, surfactant combinations are suitable as surfactants in agricultural formulations and for stabilizing aqueous emulsions and suspensions. Therefore, surfactant combinations can be assembled prior to their intended use, for example, by combining component A and component B, which are two separate components, into a corresponding composition (e.g., an agricultural chemical formulation).

[0057] However, for most purposes, it is advantageous to provide the composition as a co-formulated article containing both component A and component B. In this regard, a specific advantage of the invention is that component A is highly soluble in component B. Therefore, the compositions of the invention can be provided as a concentrated co-formulated article of components A and B (i.e., a co-formulated article containing both components A and B), wherein the total amount of components A and B is, in particular, at least 80% by weight, and especially at least 90% by weight, based on the total weight of the co-formulated article. In addition to components A and B, the concentrated co-formulated article may also contain additional ingredients such as water, organic solvents, or stabilizers. The amount of such additional ingredients is generally no more than 20% by weight, and typically no more than 10% or 5% by weight, based on the total weight of the co-formulated article. However, a solvent is not required, and the total amount of components A and B in the co-formulated article can be as high as 100% by weight, and especially at least 95% or at least 98% by weight, based on the total weight of the co-formulated article.

[0058] In co-formulated articles, the relative amounts of component A and component B are typically in the range of 10:1 to 1:10, particularly in the range of 5:1 to 1:2, and particularly in the range of 4:1 to 1:1.

[0059] In particular, co-prepared products contain

[0060] -Based on the total weight of the composition, component A comprises 9% to 90% by weight, particularly 33% to 84% by weight, and especially 50% to 80% by weight, and

[0061] - Component B, based on the total weight of the composition, comprises 9% to 90% by weight, particularly 16% to 67% by weight, and especially 20% to 50% by weight.

[0062] The co-formulated products are typically liquid at 20°C. They typically have a viscosity of no more than 11,000 mPas at 20°C, for example, in the range of 6,000 to 10,500 mPas, as measured by a Brookfield Viscometer DV2T-LV.

[0063] As previously described, the surfactant combination according to the invention is suitable as a surfactant in agricultural chemical formulations, particularly as a surfactant in liquid agricultural chemical formulations. The surfactant combination promotes the dilution of the agricultural chemical formulation in water and stabilizes the diluted solution, particularly preventing the sedimentation of solid substances contained in the agricultural chemical formulation and preventing the aggregation of any water-insoluble liquid components contained in the agricultural chemical formulation. Simultaneously, when the agricultural chemical formulation is diluted with water to the desired application concentration, the surfactant combination of the invention reduces foam formation.

[0064] For this purpose, the surfactant composition of the present invention is particularly suitable as a surfactant in liquid agrochemical formulations containing a liquid component that is immiscible with water or a substantially water-insoluble component. Therefore, the surfactant composition of the present invention is particularly suitable as a surfactant in agrochemical formulations selected from the group consisting of: emulsifiable concentrates (EC), aqueous emulsions (EW), aqueous suspensions (SE), microemulsions (ME), aqueous suspension concentrates (SC), and oil dispersions (OD).

[0065] According to a set of preferred embodiments, liquid agrochemical formulations contain a water-immiscible liquid component that must be emulsified in water before application. Therefore, the surfactant combination of the present invention is particularly suitable as a surfactant in agrochemical formulations selected from the group consisting of emulsifiable concentrates (EC), aqueous emulsions (EW), aqueous suspensions (SE), microemulsions (ME), and oil dispersions (OD).

[0066] According to another set of preferred embodiments, the liquid agrochemical formulation is a liquid multiphase aqueous formulation, wherein these phases must be stabilized to prevent aggregation or agglomeration. Therefore, the surfactant combination of the present invention is also particularly suitable as a surfactant in agrochemical formulations selected from the group consisting of: aqueous emulsions (EW), aqueous suspensions (SE), microemulsions (ME), and aqueous suspension concentrates.

[0067] Agricultural chemical formulations typically contain a combination of surfactants of the present invention in an amount typically ranging from 0.5% to 20% by weight, and particularly in an amount ranging from 1% to 10% by weight, based on the weight of the agricultural formulation. Within these ranges, those skilled in the art can readily determine the amount required for optimal stabilization of the formulation, as well as the amount required for optimal stabilization of the diluted solution obtained by diluting the corresponding agricultural chemical formulation in water to the desired application concentration.

[0068] In addition to the surfactant combination of the present invention, the agrochemical formulation also contains at least one agrochemical compound. The agrochemical compound is not particularly limited and includes pesticide compounds, pesticide safener compounds, and pesticide adjuvants. Typically, the agrochemical compound has limited water solubility in deionized water at 20°C and 1 bar, not exceeding 50 g / L, and is typically immiscible or water-insoluble as defined herein.

[0069] Pesticide compounds, particularly organic compounds from the group consisting of herbicides, fungicides, insecticides, acaricides, molluscicides, plant growth regulators, and desiccants.

[0070] Suitable fungicides include, for example, those in the following categories: dinitroaniline, allylamine, aniline pyrimidine, antibiotics, aromatic hydrocarbons, benzyl sulfonamide, benzimidazole, benzisothiazol, benzophenone, benzothiadiazole, benzotriazine, benzyl carbamate, carbamate, carboxamide, carboxylic acid amide, chloronitrile, cyanoacetamide oxime, cyanoimidazole, cyclopropaneformamide, dicarboximide, dihydrodioxazine, dinitrophenyl crotonate, dithiocarbamate, dithiopentane, ethyl phosphonate, ethylaminothiazole formamide, guanidine, hydroxy-(2-amino)pyrimidine, hydroxyaniline, isobenzo[…] Furanone, methoxyacrylate, methoxycarbamate, morpholine, N-phenylcarbamate, oxazolidinone, oxime acetate, oxime acetamide, peptidylpyrimidine nucleoside, phenylacetamide, phenyl pyrrole, phenylurea, phthalimide, piperazine, piperidine, propionamide, pyridazinone, pyridine, pyridylmethylbenzamide, pyrimidineamine, pyrimidine, pyrimidinone hydrazone, pyrroloquinone, quinazolinone, quinoline, quinone, sulfonamide, aminosulfonyltriazole, thiazolecarbamate, thiocarbamate, thiophanate-methyl, thiophenecarbamate, toluamide, triphenyltin compounds, triazine and triazole.

[0071] Suitable insecticides include, for example, those from the following categories: carbamates, phenylpyrazoles, pyrethroids, neonicotinoids, spinosin, avermectin, milbemycin, juvenile hormone analogs, nereistoxin analogs, benzoylurea, diazide, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, and etoxazole. xazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives.

[0072] Suitable herbicides include, for example, those in the following categories: acetamide, amide, aryloxyphenoxypropionate, benzamide, benzofuran, benzoic acid, benzothiadiazinone, bipyridinium, carbamate, chloroacetamide, cyclohexanedione, dinitroaniline, dinitrophenol, diphenyl ether, glycine, imidazolinone, isoxazole, isoxazolidinone, nitriles, N-phenylphthalimide, oxadiazole, oxazolidinone, oxyacetamide, phenoxycarboxylic acid, phenylcarbamate, phenylpyrazole, phenylpyrazoline, phenyl Pyridazine, aminophosphate, dithiophosphate, phthalamate, pyrazole, pyridazinone, pyridinecarboxamide, pyrimidinedione, (thio)benzoic acid pyrimidine ester, quinoline carboxylic acid, hemicarbazone, sulfonylaminocarbonyltriazolinone, sulfonylurea, tetrazolinone, thiadiazole, thiocarbamate, triazine, triazinone, triazole, triazolinone, triazolocarboxamide, triazolopyrimidine, trione, uracil, or urea. Specific examples of herbicide compounds suitable for formulation in the formulations of this invention are saflufenacil, pendimethalin, atrazine, S-metolachlor, 2,4-D ester, isoxaflutole, indaziflam, diflufenzopyr, clonzone, sulfentrazone, pyroxasulam, dimethenamid-P, cinmethylin, and pyroxaflufenacil. asulfone, toramezone, mesotrione, pinoxaden, mesosulfuron, acetochlor, clethodim, propoxycarbazone, propisochlor, bentazone, clonifen, metazachlor, flumioxazin, fomesafen, aclonifen, and diflufenican.

[0073] Pesticide safeners are organic compounds that reduce or prevent the potential phytotoxic effects of pesticides. Examples of safeners are, for example, (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide, α-oxime-phenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzamide, 1,8-naphthalenedicarboxylic anhydride, 2-halo-4-(haloalkyl)-5-thiazolic acid, thiophosphates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives, such as amides, esters and thioesters, provided that they have an acid group.

[0074] The concentration of agrochemical compounds in agrochemical formulations typically depends on the type of agrochemical compound and the type of formulation, and can be based on the total weight of the agrochemical formulation in the range of 0.1% to 70% by weight, particularly in the range of 1% to 50% by weight.

[0075] In addition to the surfactant combinations, biocidal compounds, and biocidal safeners of the present invention, the agricultural chemical formulations of the present invention may also contain one or more additional nonionic surfactants different from those having formula (I). Specifically, the additional nonionic surfactant is selected from nonionic surfactants with an HLB of at least 12 according to Griffin, for example, in the range of 12 to 18, particularly in the range of 13 to 18 or 14 to 18, as described above. In particular, these additional nonionic surfactants are selected from C16 surfactants with an ethoxylation degree of at least 20, for example, in the range of 20 to 50. 10 -C 20 Ethoxylated sorbitol monoesters of fatty acids, C8-C 10 -Alkyl polyglucoside, ethoxylated C8-C with a degree of ethoxylation of 11 to 50 20 Alkyl alcohols, ethoxylated vegetable oils with an ethoxylation degree of at least 20, for example, in the range of 20 to 50, and ethoxylated C4-C16-alkylphenols with an ethoxylation degree in the range of 11 to 50. Particularly preferred are ethoxylated C8-C16 alkylphenols with an ethoxylation degree of 11 to 50. 20Alkane alcohols, ethoxylated vegetable oils with an ethoxylation degree of at least 20, for example, in the range of 20 to 50, wherein the latter is even more preferred. In particular, the additional nonionic surfactant included in the formulation is selected from ethoxylated vegetable oils with an ethoxylation degree of at least 20, for example, in the range of 20 to 50, specifically selected from the group consisting of ethoxylated castor oil and ethoxylated soybean oil.

[0076] The concentration of the additional nonionic surfactant in agricultural chemical formulations typically depends on the type of agricultural chemical compound and the type of formulation, and can be in the range of 0% to 20% by weight, particularly 0% to 10% by weight, for example 0.1% to 20% by weight, particularly in the range of 0.5% to 10% by weight, based on the total weight of the agricultural chemical formulation.

[0077] In addition to the surfactant combination, the agrochemical compound selected from the biocidal and biocidal safeners of the present invention, and the optional additional nonionic surfactant, the agrochemical formulation of the present invention may also contain one or more liquid carriers. Suitable liquid carriers are water and organic solvents, including organic solvents immiscible with water, such as…

[0078] - Mineral oil grades with medium to high boiling points, such as kerosene and diesel;

[0079] - Aliphatic, cyclic, and aromatic hydrocarbons, such as toluene and paraffin.

[0080] - Oils of plant or animal origin, such as sunflower oil, low-erucic acid rapeseed oil, soybean oil, and mixtures thereof;

[0081] - C1-C4 alkyl esters of fatty acids, especially methyl and ethyl esters, particularly esters derived from vegetable oils;

[0082] - Fatty acid amides, especially fatty acid dimethylamides, particularly those derived from vegetable oils;

[0083] -Tetrahydronaphthalene, alkylated naphthalene;

[0084] β-Benzyl esters, such as benzyl acetate;

[0085] Organic solvents miscible with water, such as

[0086] -C2-C5 alcohols, such as ethanol, propanol, butanol, benzyl alcohol, and cyclohexanol;

[0087] - Diols, such as ethylene glycol and propylene glycol; and

[0088] - Non-protic polar solvents, such as DMSO, ketones (e.g., cyclohexanone); alkyl lactates, cyclic carbonates, γ-butyrolactone; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide;

[0089] and its mixtures.

[0090] Depending on the type of formulation, the amount of liquid carrier, based on the total weight of the agrochemical formulation, can range from 10% to 99% by weight, particularly from 15% to 98% by weight.

[0091] The agricultural chemical formulations of the present invention may additionally contain one or more other adjuvants, such as thickeners, bactericides, antifreeze agents (in the case of aqueous formulations), defoamers, colorants, and viscous agents.

[0092] Suitable thickeners include, for example, polysaccharides (such as xanthan gum and carboxymethyl cellulose), inorganic clays (which may be organically modified or unmodified), polycarboxylates, and inorganic silicates (such as fumed silica or colloidal silica). Suitable bactericides include, for example, bromonitol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents include, for example, ethylene glycol, propylene glycol, urea, and glycerin. Suitable defoamers include, for example, silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g., red, blue, or green) include, for example, low-water-soluble pigments and water-soluble dyes. Examples of inorganic pigments are iron oxide, titanium dioxide, and ferric hexacyanoferrate. Organic colorants include, for example, alizarin colorants, azo colorants, and phthalocyanine colorants. Suitable thickeners or binders include, for example, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0093] For example, a typical emulsifiable concentrate of the present invention may contain 1 to 70 wt% of at least one biocidal compound or a combination of at least one biocidal compound and a biocidal safener, 1 to 10 wt% of the surfactant combination of the present invention, and optionally 1 to 10 wt% of castor oil ethoxylate, wherein all components are dissolved in a water-immiscible organic solvent (such as aromatic hydrocarbons, vegetable oils, or mixtures thereof), wherein the amount of solvent and the other components is increased to 100 wt%. Diluting 1 part by weight of the emulsifiable concentrate with 100 parts by weight of water yields a stable emulsion.

[0094] For example, a typical aqueous emulsion of the present invention may contain 5 to 40 wt% of at least one biocidal compound or a combination of at least one biocidal compound and a biocidal safener, 1 to 10 wt% of the surfactant combination of the present invention, and optionally 1 to 10 wt% of castor oil ethoxylate dissolved in 20 to 40 wt% of a water-immiscible organic solvent (such as aromatic hydrocarbons, vegetable oils, or mixtures thereof). This mixture is introduced into 100 wt% water using an emulsifier to form a homogeneous emulsion. Diluting 1 part by weight of the resulting aqueous emulsion with 100 parts by weight of water yields a stable emulsion.

[0095] For example, a typical aqueous suspension concentrate (SC) of the present invention may contain 5 to 60 wt% of at least one biocidal compound or a combination of at least one biocidal compound and a biocidal safener in the form of particles with an average diameter in the range of 0.5 to 6 μm (as determined by dynamic light scattering), 0.5 to 20 wt% of a thickener (e.g., xanthan gum or layered silicate), and water added to 100 wt%. For SC formulations intended for seed treatment, i.e., so-called FS-type formulations, up to 40 wt% of a binder (e.g., polyvinyl alcohol) may be included in the formulation. A stable aqueous suspension is obtained by diluting 1 part by weight of the aqueous suspension concentrate with 100 parts by weight of water.

[0096] The suspension emulsion of the present invention can be obtained by mixing an aqueous suspension concentrate with an aqueous emulsion or with an emulsifiable concentrate as described herein.

[0097] A typical microemulsion of the present invention may contain 1 to 30 wt% of at least one biocidal compound or a combination of at least one biocidal compound and a biocidal safener, 5 to 30 wt% of an organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10 to 25 wt% of a surfactant blend comprising a 1:1 combination of the surfactant composition of the present invention, and water to 100%. The mixture is stirred for 1 h to spontaneously generate a thermodynamically stable microemulsion.

[0098] A typical oil dispersion (OD) of the present invention may contain 1 to 20 wt% of at least one biocidal compound or a combination of at least one biocidal compound and a biocidal safener, 50 to 80 wt% of an organic solvent blend (e.g., fatty acid dimethylamide and fatty acid methyl ester), and 5 to 25 wt% of a surfactant blend comprising the surfactant composition of the present invention and optionally a combination of co-surfactants. This mixture produces a stable dispersion.

[0099] The biocidal formulations of the present invention can be prepared by conventional procedures and typically include mixing the components of the formulation and optionally grinding and / or one or more homogenization steps.

[0100] The formulations of the present invention are typically applied as an aqueous diluent to the target organism or the ground or habitat where the target organism may be present. For this purpose, the formulations are applied in conventional ways, such as by pre-dosing devices, backpack sprayers, spray cans, spray aircraft, or irrigation systems. Typically, the formulation is supplemented with water, buffers, and / or additional adjuvants (such as auxiliaries) to the desired application concentration to obtain a ready-to-use spray or a formulation according to the invention. Typically, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray are applied per hectare of agriculturally usable area.

[0101] The formulations of this invention can be used in conjunction with adjuvants for pest control, which are compounds that themselves possess negligible or even no pest-control activity and improve the biological performance of the corresponding pest-control compound on the target organism. Examples are surfactants, mineral or vegetable oils, and combinations thereof with nonionic surfactants (such as fatty alcohol-alkoxylates). Further examples are listed in Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0102] The invention is further illustrated by the following examples.

[0103] The following abbreviations were used:

[0104]

[0105] Use the following compounds:

[0106] • Sodium dodecyl sulfate, solid powder, purity > 98% by weight;

[0107] • A 55% wt% aqueous solution of sodium dodecylbenzenesulfonate;

[0108] • 60 wt% of linear calcium dodecylbenzenesulfonate (e.g., Stepan Company's Ninate) in 2-ethylhexanol ® 60E);

[0109] • 2-Decanol, purity > 98%;

[0110] • 2-Propylheptanol, purity > 98%;

[0111] • Deionized water;

[0112] • Heptane, analytical grade;

[0113] • Decane, analytical grade;

[0114] • Compound (I) mixture: R = 2-propylheptyl compound having formula (I) wherein the number mean of n is 3, containing about 21% by weight of compound (I) wherein n = 0.

[0115] General Program

[0116] In glass vials, the appropriate surfactant or surfactant combination is mixed with a 1:1 mixture (v / v) of water and heptane or a 1:1 mixture (v / v) of water and decane, and homogenized at 25°C using a vortex mixer until the mixture is homogeneous. The mixture is then left to stand at 25°C for 2 weeks. The phase separation of the resulting emulsion is then evaluated and classified according to its Winsor type.

[0117] Comparison Example 1:

[0118] Following standard procedure, 5 wt% sodium dodecyl sulfate and 1.5% 2PH were mixed with water / heptane at a 1:1 w / w ratio. Phase separation was observed, and no microemulsion was formed.

[0119] Comparison Example 2:

[0120] Following standard procedure, 5 wt% sodium dodecyl sulfate and 2.5% 2PH were mixed with water / heptane at a 1:1 w / w ratio. Phase separation was observed, and no microemulsion was formed.

[0121] Comparison Example 3:

[0122] Following standard procedure, a 55 wt% solution of 10 wt% NaDBS in water was mixed with water / decane at a 1:1 w / w ratio. No clear intermediate phase was formed, i.e., no bicontinuous microemulsion was formed.

[0123] For reference, a commercial Ca-DDBS / 2EH mixture:

[0124] According to the general procedure, a 60 wt% solution of 2.5 wt% CaDBS in 2EH and 5 wt% urea were mixed with water / decane at a ratio of 1:1 w / w to form a Winsor type III system.

[0125] Example 1 of the present invention:

[0126] According to the general procedure, a 55 wt% solution of 10 wt% NaDBS in water and a 10 wt% mixture of compound (I) were mixed with water / decane at a ratio of 1:1 w / w to form a Winsor type IV system.

[0127] Example 2 of the present invention:

[0128] According to the general procedure, a 55 wt% solution of 10 wt% NaDBS in water and a mixture of 4 wt% of compound (I) were mixed with water / decane at a ratio of 1:1 w / w to form a Winsor type IV system.

[0129] Example 3 of the present invention:

[0130] According to the general procedure, a 55 wt% solution of 10 wt% NaDBS in water and a mixture of 3 wt% of compound (I) were mixed with water / decane at a ratio of 1:1 w / w to form a Winsor type IV system.

[0131] Example 4 of the present invention:

[0132] Following a standard procedure, a 55 wt% solution of 10 wt% NaDBS in water and 2 wt% 2-decyl alcohol were mixed with water / decane at a 1:1 w / w ratio. This formed a Winsor III microemulsion, approaching the type IV region. The microemulsion exhibited increased solubility compared to 10 wt% aqueous NaDBS without decanol.

[0133] Example 5 of the present invention:

[0134] According to the general procedure, 0.12 wt% NaDBS, 0.08 wt% mixture of compound (I), 0.2 wt% castor oil ethoxylate (25 mol EO), 0.6 wt% solvent, and 99 wt% water were mixed to form a transparent emulsion, Winsor type IV system.

Claims

1. A surfactant composition comprising a) Anionic component A, which is selected from C 10 -C 14 Sodium alkylbenzene sulfonate, and b) Non-anionic component B, which is selected from compounds having formula (I) and mixtures thereof. R-O-(CH2CH2-O) n -H](I) in R is the branch C8-C. 10 Alkyl; and n is an integer in the range of 0 to 10, and more specifically in the range of 0 to 6.

2. The surfactant combination as described in claim 1, wherein, R is 2-ethylhexyl or 2-propylheptyl.

3. The surfactant combination as described in any one of the preceding claims, wherein, Component B comprises at least 5% by weight, particularly at least 10% by weight, of a compound having formula (I) where n is 0, based on the weight of component B.

4. The surfactant combination as described in any of the preceding claims, wherein, Component B is a mixture of compounds having formula (I), comprising a compound having formula (I) wherein n is 0 and at least one other compound having formula (I) wherein n is in the range of 1 to 10, particularly in the range of 1 to 6.

5. The surfactant combination as described in any one of the preceding claims, wherein, The weight ratio of the anionic component A to the non-anionic component B is in the range of 10:1 to 1:10, particularly in the range of 5:1 to 1:

2.

6. The surfactant combination as described in any one of the preceding claims, wherein, Component A is sodium dodecylbenzenesulfonate.

7. The surfactant combination as described in any of the preceding claims, wherein the surfactant combination is a co-formulation of concentrates of component A and component B, wherein, The total amount of component A and component B is at least 80% by weight.

8. Use of the surfactant combination as described in any one of claims 1 to 7 as a surfactant in an agrochemical formulation.

9. The use of the surfactant combination as described in any one of claims 1 to 7 for stabilizing aqueous diluents of agricultural chemical formulations and / or for promoting the dilution of agricultural chemical formulations in water.

10. Use of the surfactant combination as described in any one of claims 1 to 7 for stabilizing multiphase formulations of aqueous agricultural chemicals.

11. The use as described in any one of claims 8 to 10, wherein, The agricultural chemical formulation is a liquid formulation, particularly an emulsifiable concentrate (EC), an aqueous emulsion (EW), an aqueous suspension emulsion (SE), a microemulsion (ME), an aqueous suspension concentrate (SC), or an oil dispersion (OD).

12. An agricultural chemical formulation comprising... i. The surfactant combination as described in any one of claims 1 to 7, and ii. At least one agricultural chemical compound, selected from biohazard-killing compounds, biohazard-killing safeners, and mixtures thereof.

13. The agricultural chemical formulation as claimed in claim 12, wherein the agricultural chemical formulation is a liquid formulation, particularly an emulsifiable concentrate (EC), an aqueous emulsion (EW), a microemulsion (ME), an aqueous suspension emulsion (SE), an aqueous suspension concentrate (SC), or an oil dispersion (OD).

14. The agricultural chemical formulation as claimed in any one of claims 12 or 13, wherein the agricultural chemical formulation contains the combination of surfactants in an amount ranging from 0.5% to 20% by weight, particularly in an amount ranging from 1% to 10% by weight, based on the weight of the agricultural formulation.

15. The use as described in any one of claims 8 to 11 or the agricultural chemical formulation as described in any one of claims 12 to 14, wherein, This agrochemical formulation contains an additional nonionic surfactant with an HLB of at least 12 according to Griffin, particularly ethoxylated C8-C with a degree of ethoxylation of 12 to 50. 20 Alkane alcohols or ethoxylated vegetable oils with a degree of ethoxylation of at least 20.

16. An aqueous spray solution comprising... i. The surfactant combination as described in any one of claims 1 to 7; ii. At least one agricultural chemical compound, selected from biocidal compounds, biocidal safeners, and mixtures thereof; and iii. Water.

Images