WO2019068913A1 - Formulations comprising biologically active ingredients - Google Patents

Abstract

A non-aqueous, emulsifiable formulation comprising a) at least 3 % by weight of at least one surfactant, b) at least 10 % by weight of an organic liquid, c) at least 0.1 % by weight of at least one viscosifier selected from N- hydrocarbyldiamides or mixtures thereof, and d) at least 0.5 wt% of at least one biologically active ingredient.

Description

Formulations comprising biologically active ingredients

[0001] This application claims priority to European patent application

No. 17306340.5 filed on October 5, 2017, the whole content of this application being incorporated herein by reference for all purposes.

[0002] The present invention relates to formulations comprising surfactants,

organic liquids, viscosifiers and biologically active ingredients.

[0003] The present invention relates to the field of formulations comprising

biologically active ingredients, for example compositions comprising pharmaceutically active compositions and agriculturally active

compositions.

[0004] Agriculturally active ingredients like agricultural pesticides, including

insecticides, fungicides, herbicides, miticides and plant growth regulators as well as tank-mix adjuvants or fertilizers are generally produced in pure or highly concentrated form. However, they are to be used on agricultural operation sites in low concentration. To this end, they are usually formulated with other ingredients that enable easy dilution by the farm operator. The dilution is generally performed by mixing the agricultural concentrated formulation with water.

[0005] Two kinds of formulations represent the largest sales volumes which are emulsifiable concentrates (EC) and suspensions concentrates (SC). Such concentrated formulations are advantageous since they are easy to prepare, they have a high concentration in active material, a good stability, a high biological activity, and they are cheap. However, emulsifiable concentrates (which comprise an active agent dissolved in an organic solvent) need to use organic solvents like for example xylene, naphtalene and N-methylpyrrolidone which are potentially dangerous regarding environment and human health. In contrast, suspensions concentrates (which are stable suspensions of active agents in an aqueous liquid and are safe and easy to manipulate) are not sufficiently effective and not convenient for active agent which are sensible to water.

[0006] To solve these drawbacks a third type of formulation has been developed, namely oil dispersions. This type of compositions consists in a suspension of active material(s) in an apolar medium, generally an oily fluid intended to be diluted with water before use. WO2013/043678 discloses some concentrate formulations that can be readily combined with pesticide to form an oil dispersion which subsequently may be diluted, in particular by a farm operator, with water to form the corresponding pesticide emulsion. These prior art formulations include as oily vehicle at least one vegetable oil alkyl ester.

[0007] WO 2016/142518 discloses concentrate formulations comprising at least 20 % by weight of at least one non-ionic surfactant chosen from

polyethylene glycol esters of fatty acids surfactants, relative to the total weight of the concentrate formulation, a liquid medium wholly or partly formed from at least one non esterified vegetable oil or mixtures thereof, at least one phyllosilicate, said phyllosilicate being present in a content of less than or equal to 5 % by weight relative to the total weight of the concentrate formulation and at least one activator of said phyllosilicate.

[0008] There is still a need for further formulations comprising biologically active ingredients suitable for use in various applications.

[0009] It was thus an object of the present invention to provide formulations

comprising biologically active ingredients with good application properties

[0010] This object is achieved by the formulations in accordance with claim 1.

[001 1] Preferred embodiments of the formulations in accordance with the present invention are set forth in the dependent claims and in the detailed specification hereinafter.

[0012] A further embodiment of the invention is directed to the use of the

formulations in accordance with the invention as pharmaceutical or agricultural compositions.

[0013] A still further embodiment of the invention relates to a method for

preventing or combatting diseases in animals, such mammals, or for preventing or combatting infestation of plants by pests and/or of regulating plant growth, comprising the application of a mixture obtained by diluting a formulation according to the invention.

[0014] For the purpose of the present invention, the term "emulsifiable" means a composition that forms an emulsion when diluted into water and mixed by inversion of the vial. Preferably, after 10 inversions of the vial (CIPAC MT36 and MT180) such emulsion is stable at least 30 minutes, and in particular two hours after its formation ("stable" meaning that no or only little phase separation of cream is observed)

[0015] The formulations in accordance with the invention comprise as component at least 3 wt%, based on the total weight of the formulation, of at least one surfactant.

[0016] According to preferred embodiments the formulation comprises 3 to 50, preferably 5 to 40 and more preferably 10 to 35 wt% of a surfactant.

[0017] For the purpose of the present invention, the term "surfactant" means a compound that, when present in water, lowers the surface tension of water. Surfactants may act as detergents, wetting agents, surfactants, foaming agents, and dispersants.

[0018] Surfactants can be generally grouped into ionic and non-ionic

representatives. For the formulations according to the invention, non. ionic surfactants are generally preferred.

[0019] In accordance with a preferred embodiment, the surfactant is selected from the group consisting of anionic surfactants, cationic surfactants, non- ionic surfactants, amphoteric surfactants or alkoxylated derivatives of anionic surfactants, cationic surfactants or amphoteric surfactants.

[0020] Ionic surfactants can be characterized by the ionic nature of at least part of their hydrophilic moiety (possibly, all) their hydrophilic moiety(-ies). Thus, the hydrophilic moiety(-ies) of ionic surfactants, also named "head", can be anionic (the corresponding surfactants being referred to as "anionic surfactants") or cationic (the corresponding surfactants being referred to as "cationic surfactants"). For the avoidance of doubt, surfactants of mixed ionic-non ionic nature, which further comprise at least one non ionic moiety in addition to the at least one ionic moiety, wherein said non ionic moiety is optionally directly connected to said ionic moiety, are also understood as ionic surfactants for the purpose of the present invention.

[0021] When the surfactant is anionic, the at least one hydrophilic moiety is

advantageously selected from the group consisting of sulfates (-O-SO3^"), sulfonates (-SO3^" ). carboxylates [C(=O)O- ] and mixtures thereof (as it is the case e.g. for sulfosuccinate-type surfactants).

[0022] Usually, in carboxylates of formula R-C(=O)OX, R is C₈-C₂o alkyl or C₈-C₂o alkenyl (such as oleyl) and X is an ammonium or an alkali metal. As examples of alkyl carboxylates, it can be cited sodium laurate, ammonium myristate, sodium stearate. Other carboxylates, based on a C8-C20 hydrocarbyl lipophilic moiety other than alkyl or alkenyl, can also be useful, for example sodium abietate.

[0023] Sulfonates include e.g. primary alkyl or alkenyl sulfonates and secondary alkyl or alkenyl sulfonates. Usually, in primary alkyl sulfonates of formula R-SO3X, R is C8-C20 alkyl and X is an ammonium or an alkali metal; as an example thereof, it can be cited Ci6H3i-SOsNa. In general, in secondary alkyl sulfonates of formula R-CH(-SO₃X)-R\ R and R' are C -C₂o alkyl, the total number of carbon atoms of R and R' ranges from 7 to 29 and X is an ammonium or an alkali metal; as an example thereof, if can be cited CH₃(CH2)n-CH(SO₃Na)-(CH2)m-CH3 wherein m+n=13.

[0024] Other sulfonates, based on a C8-C20 hydrocarbyl lipophilic moiety other than alkyl, can also be useful.

[0025] As examples for sulfates alkyl sulfates and alkenyl sulfates may be

mentioned. Usually, in sulfates of formula R-OSO3X, R is C8-C20 alkyl or C8-C20 alkenyl (such as oleyl) and X is an ammonium or an alkali metal. As examples of alkyl sulfates, it can be cited sodium hexyl sulfate, sodium palmityl sulfate and sodium, ammonium or lithium lauryl sulfate.

[0026] As examples of sulfosuccinates, monoalkyl sulfosuccinates of formula

R-O-C(=O)-CH₂-CH(SO₃X)-C(=O)OX'

wherein R is C8-C20 alkyl and X and X' are independently ammonium or an alkali metal may be mentioned.

Dialkyl sulfosuccinates are typically of formula

R-O-C(=O)-CH₂-CH(SO₃X)-C(=O)OR'

wherein R and R' are independently C₄-C2o alkyl, the total number of carbon atoms of R and R' ranges from 8 to 40 and X is ammonium or an alkali metal. As examples thereof, it can be cited sodium di-[(2-ethyl)- hexyl]sulfosuccinate and sodium diisodecylsulfosuccinate.

[0027] Monoalkyl sulfosuccinamates are typically of formula R-HN-C(=O)-CH₂-CH(SO₃X)-C(=O)OX'

wherein R is C8-C20 alkyl and X and X' are independently ammonium or an alkali metal.

Dialkyi sulfosuccinamates are typically of formula

R-HN-C(=O)-CH₂-CH(SO₃X)-C(=O)OR'

wherein R and R' are independently C₄-C2o alkyl, the total number of carbon atoms of R and R' ranges from 8 to 40 and X is ammonium or an alkali metal.

[0028] MonoalkyI and dialkyi phosphates of respective formulae R-O-P(=O)-(OX)2 and R₂-O-P(=O)-OX wherein R is C -C₂o alkyl (preferably, C₈-C₂o alkyl) and X and X' are independently ammonium or an alkali metal may be mentioned as further suitable anionic surfactants.

[0029] There are other groups of anionic surfactants known to the skilled perosn and which have been decribed in the prior art. The skilled person will select the best suitable surfactant based on his professional knowledge and the specific application case, so that no further details need to be given here.

[0030] Exemplary representatives of cationic surfactants are monoalkyl and

dialkyi phosphates of respective formulae R-O-P(=O)-(OX)2 and R2-O- P(=O)-OX wherein R is C -C₂o alkyl (preferably, C₈-C₂o alkyl) and X and X' are independently ammonium or an alkali metal, monoalkyl and dialkyi phosphates of respective formulae R-O-P(=O)-(OX)₂ and R₂-O-P(=O)-OX wherein R is C₄-C₂o alkyl (preferably, Cs-C₂o alkyl) and X and X' are independently ammonium or an alkali metal, quaternary ammonium or pyridinium salts.

[0031] The ionic surfactant, which can be cationic or anionic, may further include at least one non ionic hydrophilic moiety. Sometimes, the additional non ionic moiety is directly connected to an ionic moiety of the ionic surfactant, and can therefore form a combination of hydrophilic moieties of mixed ionic-non ionic nature, such as in oxyalkylene sulfates of formula -O-A_y- SO3^" wherein A denotes an oxyalkylene unit (e.g. CH₂CH₂O, CH₂CH₂CH₂O or CH₂CH(CH3)O or combinations thereof) and y ranges from 2 to 50.

[0032] The non ionic moiety consists generally of one or more C₂-C₄ oxyalkylene units, preferably oxyethylene and/or oxypropylene units, and more preferably oxyethylene units. The total number of oxyalkylene units in the ionic surfactant generally is in the range of from 2 to 50, preferably of from 3 to 25 and even more preferably of from 4 to 12.

[0033] Exemplary representatives of alkoxylated ionic surfactants are ether

carboxylates of formula R-O-Ay-Ch -COOX wherein R is C8-C20 alkyl or C8-C20 alkenyl (such as oleyl), A is a oxyalkylene unit (e.g. CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50.

[0034] Other examples are ester carboxylates of a di-, tri- or tetracarboxylic acid, and are obtainable by the condensation reaction of an alcohol with the di-, tri- or tetracarboxylic acid (e.g. glycolic acid, citric acid or tetrabutane carboxylic acid), wherein the alcohol has been previously alkoxylated. Further mentioning may be made of ether sulfonates of formula

R-O-Ay-CH2-SO3X wherein R is C8-C20 alkyl or C8-C20 alkenyl (such as oleyl), A is a oxyalkylene unit (e.g. CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50, alkyl or alkenyl ether sulfates of formula R-O-Ay-SOsX wherein R is C8-C20 alkyl or alkenyl (such as oleyl), A is a oxyalkylene unit (e.g. -CH2CH2O-), X is ammonium or an alkali metal and y ranges from 2 to 50, alkoxylated sulfosuccinates, such as the alkoxylated sulfosuccinates of formula

R-O-A_y-C(=O)-CH₂-CH(SO₃X)-C(=O)OX'

wherein R is C8-C20 alkyl, A is a oxyalkylene unit (e.g. CH2CH2O), X and X' are independently ammonium or an alkali metal and y ranges from 2 to 50, and monoalkyl and dialkyl ether phosphates of respective formulae R-O- Ay-P(=0)-(OX)₂ and (R-A_y)₂-O-P(=O)-OX, R is C₈-C₂o alkyl, A is a oxyalkylene unit (e.g. CH2CH2O), X is ammonium or an alkali metal and y ranges from 2 to 50.

[0035] As mentioned hereinabove, non-ionic surfactants are preferred for the

purpose of the present invention, and same will now be described in some more detail.

[0036] Non-ionic surfactant are usually selected from the group comprising ether- based non-ionic surfactants, ester-based non-ionic surfactants, amine- based or amide-based non-ionic surfactants and fluoro-surfactants. [0037] Ether based non ionic surfactants: Ethers of carboxylic acids-based non- ionic surfactants, alcohol-based non-ionic surfactants, oside-based non- ionic surfactants, fatty alcohol-based non-ionic surfactants and silicone non-ionic surfactants may be mentioned as examples.

[0038] Non-ionic surfactants of interest in accordance with the present invention may be represented by ethers of carboxylic acids of the following formula:

[0039] R¹⁰-O-(R -O)y-CH₂-COOH ,

[0040] wherein R ⁰ is C₈-C₂o alkyl, C₈-C₂o alkyl phenyl or C₈-C₂o alkenyl, R is C₂-Cio alkylene, for example -CH₂-CH₂-, -CH₂-CH₂-CH₂- or a mixture thereof, and y ranges from 2 to 50.

[0041] In particular, ethers of carboxylic acids-based non-ionic surfactants are preferably represented by polyoxyethylene-based non-ionic surfactants (- (CH₂-CH₂-O)-), polyoxypropylene-based non-ionic surfactants (-(CH2-CH₂- CH₂-O)-), polyoxyethylene-polyoxypropylene -based non-ionic surfactants.

[0042] A polyoxyethylene-based nonionic surfactant may comprise a

polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene polyoxypropylene alkyl ether.

[0043] Among polyoxyethylene alkyl ethers, one may cite compounds such as polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene isostearyl ether.

[0044] Among polyoxyethylene alkyl phenyl ethers, one may cite compounds such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and dialkylphenoxy poly(ethyleneoxy) ethanol.

[0045] Among polyoxyethylene polyoxypropylene alkyl ether, one may cite

compounds such as polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyltetradecyl ether.

[0046] Alcohol-based non-ionic surfactants of interest in accordance with the

present invention may be represented by alkoxylated alcohols.

[0047] Within the scope of the present invention, the term "alkoxylated" relies upon the presence of oxyalkylene units, for which the total number of these units generally ranges from 2 to 50, preferably from 3 to 25, preferably from 4 to 12, preferably from 2 to 10, most preferably from 2 to 6, or, in accordance witn another embodiment, preferably from 10 to 50, most preferably from 10 to 35.

[0048] Alkoxylated alcohols of interest may be represented by a compound of the general formula as follows:

[0049] R² -O-(R²²-O)y-H

[0050] wherein R² is C6-C30 hydrocarbyl, preferably C8-C20 alkyl or C8-C20

alkenyl, more preferably octyl or nonyl, R²² is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0051] Examples of alkoxylated alcohols suitable as a non-ionic surfactant,

according to the invention, are the products of the condensation of (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide, with (ii) a mole of a saturated or unsaturated (preferably ethjylenically unsaturated) fatty alcohol, especially a C8-C20 alcohol chosen from lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, oxoalcohols and mixtures thereof.

[0052] Other examples of alkoxylated alcohols suitable as a non-ionic surfactant, are the products of condensation of (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide, with a mole of n- octylphenol, n-nonylphenol and mixtures thereof.

[0053] Alcoxylated alcohols may be commercially available under the tradenames Brij® (Atlas Chemical Co.), Genapol® (Clariant) and Lutensol® (BASF).

[0054] Oside-based nonionic surfactants may comprise long chain alkyl

polyglucosides, which are obtained by the condensation of a) a long chain alcohol containing from about 6 to about 25 carbon atoms, with b) a glucose or glucose containing polymer. In practice such a compound may be alkyl polyglycosides and alkyl polysaccharides, such as decyl glucoside, octyl glucoside, decyl maltoside or alkylpolyxylosides.

[0055] Alkoxylated phenol surfactants are also suitable and alkoxylated

alkylphenols, alkoxylated alkylarylphenols, alkoxylated sulfated and/or phosphate alkylphenols and alkoxylated sulfated and/or phosphate alkylarylphenols may be mentioned n this regard. [0056] An alkoxylated phenol compound that is suitable comprises an

oxyalkylene group that may be for instance an oxyethylene group, an oxypropylene group, or an oxyethylene/ oxypropylene group (i.e. ethoxy- propoxylated group). The number of oxyalkylene units, such as the number of oxyethylene (OE) units and/or oxypropylene (OP) units, in the alkoxylated phenol compound is normally between 2 and 100 depending on the desired HLB (hydrophile/lipophile balance). More particularly, the number of OE and/or OP units is comprised between 2 and 50. Preferably, the number of OE and/or OP units is comprised between 5 and 50.

[0057] Alkoxylated phenol compounds suitable for the present invention may

comprise one, two or three linear or branched hydrocarbon group(s), preferably comprising from 4 to 50 carbon atoms, more preferably comprising from 4 to 12 carbon atoms, connected to the phenol group. This hydrocarbon group is preferably a hydrocarbon group chosen in the group consisting of an alkyl group, such as tert-butyl, butyl, or isobutyl; an aryl group; an alkylaryl group; and an arylalkyl group, which may comprise a heteroatom such as N, O or S. The alkyl moiety of the alkylaryl group or the arylalkyl group may be a C1-C6 alkyl moiety. Hydrocarbon group may notably be represented by a phenyl group or a phenylethyl group.

[0058] Alkoxylated phenol compounds of the present invention may notably be chosen in the group consisting of nonylphenol ethoxylated with 2 OE units; nonylphenol ethoxylated with 4 OE units; nonylphenol ethoxylated with 6 OE units; nonylphenol ethoxylated with 9 OE units; nonylphenol ethoxy- propoxylated with 25 OE+OP units; nonylphenol ethoxy-propoxylated with 30 OE+OP units; nonylphenol ethoxy-propoxylated with 40 OE+OP units; nonylphenol ethoxy-propoxylated with 55 OE+OP units; nonylphenol ethoxy-propoxylated with 80 OE+OP units; di(1 -phenylethyl)phenol ethoxylated with 5 OE units; di(1 -phenylethyl)phenol ethoxylated with 7 OE units; di(1 -phenylethyl)phenol ethoxylated with 10 OE units; tri(1 - phenylethyl)phenol ethoxylated with 8 OE units; tri(1 -phenylethyl)phenol ethoxylated with 16 OE units; tri(1 -phenylethyl)phenol ethoxylated with 20 OE units; tri(1 -phenylethyl)phenol ethoxylated with 25 OE units; tri(1 - phenylethyl)phenol ethoxylated with 40 OE units; tri(1 -phenylethyl) phenols ethoxy-propoxylated with 25 OE+OP units; ethoxylated and sulfated di(1 -phenylethyl)phenol comprising 5 OE units; ethoxylated and sulfated di(1 -phenylethyl)phenol comprising 7 OE units; ethoxylated and sulfated di(1 -phenylethyl)phenol comprising 15 OE units; ethoxylated and sulfated di(1 -phenylethyl)phenol comprising 16 OE units; ethoxylated and sulfated tri(1 -phenylethyl)phenol comprising 16 OE units; and ethoxylated and phosphated tri(1 -phenylethyl)phenol comprising 16 OE units.

[0059] Alkoxylated phenol surfactants according to the invention may be selected among :

- Tristyryl phenol ethoxylates, such as the commercially available products Soprophor ^® BSU; Soprophor ^® CY8; Soprophor ^® S25 (Solvay);

- Alcool Ethoxylates, such as the commercially available products

Rhodasurf ^® LA 12/80; Rhodasurf ^® LA 12; Rhodasurf ^® BC 720;

Rhodasurf ^® BC 630; Rhodasurf ^® BC 639 (Rhodia);

- Alkyl Phenol Ethoxylate such as the commercially available products Igepal ^® RC 630; Igepal ^® DM 530; Igepal ^® RC 620; Igepal ^® CO 610; Igepal ^® CO 630; Igepal ^® CO 660; Igepal ^® CO 710; Igepal ^® CO 710 (Solvay).

[0060] Among ester-based non-ionic surfactants of interest, one may cite

alkoxylated oils and fats. These compounds encompass ethoxylated and/or propoxylated derivatives of lanolin (wool fat) or of castor oil. Lanolin is the generic name of a wax containing a mixture of esters and polyesters of high-molecular-weight alcohols and fatty acids. Castor oil is a mixture of a triglyceride of fatty acids.

[0061] Other examples of ester-based non-ionic surfactants may be represented alkoxylated acids, such as the compounds represented by monoesters and diesters.

[0062] Monoesters of interest may be represented by a compound of the general formula as follows:

[0063]

[0064] wherein R³ is C6-C30 hydrocarbyl, preferably C8-C20 alkyl or C8-C20 alkenyl, R³² is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0065] Examples of alkoxylated acids monoesters are the condensation products of from 2 to 50 moles (in particular, from 4 to 16 moles) of an alkylene oxide (such as ethylene oxide) with one mole of a saturated or

unsaturated fatty acid chosen from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid.

[0066] An example thereof is Deplastol^® product which is a condensate of about

4-5 mol oxyethylene units with lauric acid and/or myristic acid (Cognis,

Germany). Corresponding propoxylated and/or butylated fatty acids may also be included in the alkoxylated acids monoesters of interest.

[0067] Diesters of interest may be represented by a compound of the general formula (8) as follows

[0068] wherein R⁴ and R⁴³ are independently a C6-C30 hydrocarbyl, prefreably a C8-C20 alkyl or C8-C20 alkenyl , R2 is C2-C10 alkylene, for example -CH2- CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.

[0069] Other examples of ester-based non-ionic surfactants of interest may

represented by alkoxylated glycol, such as alkoxylated ethylene glycol esters and alkoxylated propylene glycol esters.

[0070] Alkoxylated ethylene glycol respectively propylene glycol esters may be represented by a compound of the general formula as follows

[0071] wherein R⁵¹ is C8-C20 alkyl or C8-C20 alkenyl, R⁵² is hydrogen or methyl and R⁵³ is C2-C10 alkylene, for example -CH2-CH2-, -CH2-CH2-CH2-, -CH₂- CH(CH3)- or a mixture thereof, and y ranges from 2 to 50. [0072] Alkoxylated esters of monoglycerides, dialkoxylated esters of diglycerides and trialkoxylated esters of triglycerides may also be compounds of interest, said esters being the reaction products of glycerol, or one of its derivatives, with a carboxylic acid comprising from 8 to 20 carbon atoms and comprise in total from 6 to 60 oxyalkylene units.

[0073] Among the non limitating ester-based non-ionic surfactants, one may cite polyoxyethylene alkylesters, polyoxyethyleneglycerine aliphatic acid esters, polyoxyethylene castor oil, hydrogenated castor oil,

polyoxyethylene sorbitol aliphatic acid esters, polyethylene glycols aliphatic acid esters, aliphatic acid monoglycerides, polyglycerine aliphatic acid esters, sorbitan aliphatic acid esters, polyoxyethylene sorbitan aliphatic esters, propylene glycol aliphatic acid esters, cane sugar aliphatic acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters,

polyoxyethylene castor oil, polyoxyethylene cured castor oil,

polyoxyethylene cured castor oil fatty acid ester, sucrose fatty acid esters, polyoxyalkylenated fatty acid esters, oxyalkylenated alkyl polyglycosides, alkyl glucoside esters.

[0074] In particular, among polyoxyethylene glycerin fatty acid esters, one may cite polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monooleate, and polyoxyethylene glyceryl monoisostearate.

[0075] Among polyoxyethylene sorbitan fatty acid esters, one may cite

polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate.

[0076] Among polyoxyethylene sorbitol fatty acid esters, one may cite

polyoxyethylene sorbitol monolaurate.

[0077] Among polyethylene glycol fatty acid esters, one may cite polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol monolaurate. [0078] Amine-based or amide based non-ionic surfactants are alo suitable and octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, iso- dodecyldimethyl amine oxide, tridecyldimethylamine oxide,

tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylaine oxide, dodecyldipropylamine oxide,

tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,

tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2- hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1 - hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi- (2-hydroxyethyl)amine oxide may be mentioned in this regard.

[0079] Among the amide-based non-ionic surfactants, one may cite

aldobionamides, aliphatic acid alkanolamides, polyoxyethylene

alkylamides, polyoxyethylene aliphatic acid amides.

[0080] Other examples of amide-based non-ionic surfactants of interest in

accordance with the present invention may be represented by alkoxylated alkanolamides, such as alkoxylated monoalkanolamides and dialkoxylated dialkanolamides.

[0081] In accordance with a preferred embodiment, the surfactant comprises at least two C2-10 oxyalkylene moieties and is free of any components containing one or more aromatic rings.

[0082] Particularly preferred as surfactants in the formulations according to the invention are polyethylene glycol esters of fatty acids.

[0083] Representative thereof are polyethylene glycol fatty acid monoesters and polyethylene glycol fatty acid diesters, more typically mono- and di-esters of polyethylene glycols and saturated or unsaturated (C8-C22), more typically (C12-C18), fatty acids and mixtures thereof, such as for example, poly(ethylene glycol) monomyristates, poly(ethylene glycol)

monostearates, poly(ethylene glycol) distearates, poly(ethylene glycol) monooleates, poly(ethylene glycol) dioleates, poly(ethylene glycol) linolenates, poly(ethylene glycol) dibehenates, poly(ethylene glycol) monobehenates, poly(ethylene glycol) monoerucates, and their mixtures.

[0084] Examples of suitable polyethylene glycol esters of fatty acids are

commercialized by Solvay under the names Alkamuls^® AP, Alkamuls^® A, Alkamuls^® VO/2003 and Alkamuls^® VO2005.

[0085] Alkamuls^® VO/2003 and Alkamuls^® VO2005 are particularly preferred

according to the present invention.

[0086] The specific surfactant used according to the invention contributes to the obtention of a pourable concentrate, and facilitates emulsification when the concentrate is placed in the presence of water. It also provides stabilization over time of the so-formed emulsion by limiting, or even avoiding, phase separation.

[0087] As component b) the formulations according to the invention comprise an organic liquid or, more generally, an organic liquid medium. For the purpose of the present invention, "liquid medium" means a medium that is in the liquid phase at room temperature and a pressure of one

atmosphere.

[0088] The choice of organic liquid is not subject to particular limitations and the skilled person will select a suitable organic solvent based on his

professional expertise and the specific application case so that no furher details need to be given here. Suitable organic liquids have been described in the literature and are commercially available.

[0089] According to an embodiment, the solvent used in the mixture (S) according to the invention is a good solvent and can be a polar solvent or a mixture of a polar solvent and an apolar solvent.

[0090] Just by way of example, alcohols having from 1 to 10 carbon atoms, preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol or ethylhexanol may be mentioned here.

[0091] Another group or organic liquids which may be mentioned, areacetal

derivatives having from 2 to 12 carbon atoms, and is preferably selected from the Augeo^® family of solvents (available from Solvay SA) such as Augeo^® SL191 which is a racemic mixture of (+/-)-2,2-dimethyl-4- hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol.

[0092] Further examples are selected from alkyl esters having from 2 to 12

carbon atoms, preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, octyl acetate or from mixtures of (i) alcohols having from 1 to 10 carbon atoms (preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol, ethylhexanol), (ii) alkyl esters having from 2 to 12 carbon atoms (preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, octyl acetate) and (iii) acetal derivatives having from 2 to 12 carbon atoms (preferably selected from the Augeo^® family of solvents (available from Solvay SA) such as Augeo^® SL191 which is a racemic mixture (+/-)-2,2-dimethyl-4-hydroxymethyl-1 ,3-dioxolane, also known as isopropylidene glycerol).

[0093] Also mentioned here maybe esterified or non esterified mineral oils,

vegetable oils, animal oils or synthetic oils.

[0094] Preferred organic liquids as component b) are non-esterified vegetable oils or mixtures thereof.

[0095] For the purpose of the present invention, "non-esterified vegetable oil" means a native vegetable oil that is chemically not transformed and in particular not esterified. In other words, it is equivalent to its natural form. Within the context of the present invention non-esterified vegetable oils are understood to be triglycerides or mixtures of triglycerides.

[0096] More particularly, this vegetable oil or mixtures thereof constitutes the

liquid phase of the formulation and is dedicated to vehicle at least the surfactant and the viscosifier.

[0097] These vegetable oils may be selected for example from the group

consisting of soybean oil, corn oil, cottonseed oil, sunflower oil, maize oil, rice oil, olive oil, linseed oil, rapeseed oil, canola oil, palm oil, coconut oil and mixtures thereof.

[0098] Rapeseed oil, canola oil, soybean oil and corn oil are particularly

convenient for the invention. [0099] The formulation according to the invention may preferably contain from 10 to 90 % by weight, for instance from 40 to 85 % by weight, in particular from 40 to 80 % by weight, for instance from 50 to 75 % by weight relative to its total weight, of an organic liquid as component b), and in particular of a non-esterified vegetable oil or mixtures thereof.

[00100] The formulations according to the invention comprise as component c) at least 0.1 wt% of a viscosifier selected from N-hydrocarbyldiamides of general formula (I)

wherein

R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that either R^a or R^b is hydrogen,

R^c is selected from cyclic or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 25 carbon atoms.

[00101] In accordance with a preferred embodiment of the invention, the viscosifier is a N-hydrocarbyldiamide composition comprising

c1 ) a compound of formula (la)

wherein

R is a linear or branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms,

R² is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 1 to 15 carbon atoms, and

R³ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms, and c2) a compound of formula (lb)

wherein

R⁴ is a linear or branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms,

R⁵ is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 1 to 15 carbon atoms, and

R⁶ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms.

[00102] In the compounds of formula (I) R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that one and only one of R^a or R^b is hydrogen.

[00103] R^c in formula (I) is selected from cyclic or branched, saturated or

unsaturated, hydrocarbon aliphatic chains having from 2 to 25 carbon atoms.

[00104] Within the meaning of the present invention, the term "hydrocarbon chain", is to be understood as a hydrocarbon chain comprising carbon atoms and hydrogen atoms, wherein said hydrocarbon chain may optionally be substituted by one or more heteroatoms, such as oxygen atoms.

[00105] The term "aliphatic chain", is to be understood as a non-aromatic chain.

[00106] According to an embodiment of the invention, R^a or R^b of the compound of formula (I) is a hydrocarbon chain constituted only by carbon atoms and hydrogen atoms.

[00107] According to an embodiment of the invention, R^a or R^b of the compound of formula (I) is aromatic. In particular, R^a or R^b may be selected from phenyl or furyl groups. [00108] According to another embodiment of the invention, R^a or R^b of the compound of formula (I) is a linear, branched or cyclic aliphatic (non- aromatic) hydrocarbon chain.

[00109] According to an embodiment of the invention, R^a or R^b is selected from a linear or branched, saturated or unsaturated, hydrocarbon chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 10] According to an embodiment of the invention, R^a or R^b is selected from a linear, unbranched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 1 1] According to an embodiment of the invention, R^a or R^b is selected from a linear unbranched saturated hydrocarbon aliphatic chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[001 12] According to an embodiment of the invention R^a or R^b is selected from pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, 12-hydroxy stearyl, oleyl, 12-hydroxyloleyl, linoleyl, linolenyl, arachidyl, behenyl or erucyl groups.

[001 13] According to an embodiment of the invention, R^c is not cyclic. Preferably, R^c is selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 1 to 14 carbon atoms and a side chain having from 1 to 6 carbon atoms. Preferably, R^c is selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 2 to 8 carbon atoms and a side chain having from 1 to 4 carbon atoms.

[001 14] According to an embodiment of the invention, R is selected

from -CH(CH₃)-CH₂-; -CH₂-CH(CH₃)- ; -CH(CH₃)-CH₂-CH₂- ; -CH(CH₂- CH₃)-CH₂- and -CH₂-CH₂-CH(CH₃)-.

[001 15] Preferably, the compounds of formula (I) according to the invention do not present urea functions of type -NH-CO-NH-. [001 16] If the viscosifier is a N-hydrocarbyldiamide composition comprising compounds of formula (la) and (lb), the molar ratio of the compound of formula (la) to compound (lb) is preferably in the range of from 70:30 to 99: 1 , preferably in the range of from 75:25 to 98:2, more preferably of from 85: 15 to 97:3 and most preferably of from 90:10 to 97:3.

[001 17] In the N-hydrocarbyldiamide composition used as viscosifier, the

aggregated weight proportion of compounds (la) and (lb) is preferably at least 50 wt%, further preferably at least 80 wt%, more preferably at least 90 wt% of the total weight of the composition. Even more preferably the N- hydrocarbyldiamide composition essentially consists of compounds (ia) and (lb) or consists of compounds (la) and (lb).

[001 18] Preferred in accordance with the invention as viscosifiers are N- hydrocarbyldiamide compositions in which R is identical to R⁴, R² is identical to R⁵ and R³ is identical to R⁶, i.e. the N-hydrocarbyldiamide composition is preferably an isomer mixture.

[001 19] According to an embodiment of the invention, R¹ or R⁴ of the compound of formula (la) respectively formula (lb) is a hydrocarbon chain constituted only of carbon atoms and hydrogen atoms.

[00120] According to another embodiment of the invention, R or R⁴ of the

compound of formula (la) respectively formula (lb) is a linear, branched or cyclic aliphatic (non-aromatic) hydrocarbon chain.

[00121] According to an embodiment of the invention, R or R⁴ is selected from a linear or branched, saturated or unsaturated, hydrocarbon chain having from 2 to 40 carbon atoms, preferably from 4 to 32 carbon atoms, more preferably from 5 to 24 carbon atoms, even more preferably from 6 to 18 carbon atoms.

[00122] Just by way of example, R¹ and/or R⁴ can preferably be selected from

pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, palmityl, stearyl, 12-hydroxy stearyl, oleyl, 12-hydroxyloleyl, linoleyl, linolenyl, arachidyl, behenyl or erucylgroups.

[00123] R² and/or R⁵ are preferably selected from hydrocarbon aliphatic chains comprising a hydrocarbon main chain having from 1 to 14 carbon atoms. R² and/or R⁵ preferably comprise from 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms and still more preferably 1 to 2 carbon atoms

[00124] Besides, R² and/or R⁵ are preferably selected from (i) linear alkylene

chains and (ii) from linear alkylene chains substitued by one and only one linear alkyl group, wherein the linear alkyl group substituent comprises a number of carbon atoms that is preferably lower, more preferably does not comprise more than half of the carbon atoms of the linear alkylene chains and more preferably does not exceed two and more preferably does not exceed one carbon atom. More preferably, R² and/or R⁵ are linear alkylene chains.

[00125] Most preferably, R² and/or R⁵ are methylene.

[00126] Other possible choices for R² and/or R⁵ include

-(CH₂)i-, wherein I is 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 1 or 2

-CH(CH₃)-(CH₂)j- wherein j is 1 , 2, 3, 4, 5, 6, 7, 8 or 9, preferably 1 or 2 and

-(CH2)k-C(CH3)-(CH2)k'- wherein k and k' are integers equal to or exceeding 1 and the sum of k and k' is 2, 3, 4, 5, 6, 7, 8, or 9.

[00127] R² and R⁵ may also be; -CH(CH₂-CH₃)-CH₂-.

[00128] R³ and R⁶ are linear or branched alkyl groups with 1 to 8, preferably 1 to 4 carbon atoms, most preferably R³ and R⁶ are methyl.

[00129] Preferably, the compounds of formula (la) and (lb) forming the N- hydrocarbyldiamide composition according to the invention do not present urea functions of type -NH-CO-NH-.

[00130] The compounds of formula (I) or the compositions comprising the

compounds of formula (la) and (lb) may be obtained by a process wherein at least one amine and at least one reactant selected from an imide, a diacid, a diester, a primary diamide, an ester amide, an acid ester or other combinations are reacted.

[00131 ] A preferred process for manufacturing the N-hydrocarbyldiamide

compositions comprising compounds (la) and (lb) used as viscosifier in one embodiment according to the invention comprises the steps of a) the reaction between an amine and a reactant selected from an imide, a diacid, a diester, a primary diamide, an ester amide or an acid ester, and thereafter

b) subjecting the reaction product obtained in step a) to at least two cycles of recrystallization and washing steps. With increasing number of recrystallization cycles, the ratio of compounds of formula (la) and (lb) increases, if (la) and (lb) are isomers of the same N-hydrocarbyldiamide.

[00132] Ammonia may also be added during the process if it is not already present in the molecule as amide or imide functions. Ammonia may allow favoring the manufacture of the mono-alkyl form (versus the dialkyl form) of the diamide and may also allow favoring the elimination of by-products formed during the reaction (such as alcohol coming from reaction with ester as a co-product).

[00133] General processes for manufacturing diamides are described in WO

2010/031867.

[00134] In particular, the process for manuifacture of the viscosifier comprises the direct reaction between a cyclic imide and an amine.

[00135] The compounds of formula (I), (la) and/or (lb) can thus be obtained by an imide ring-opening reaction of the cyclic imide with addition of the amine.

[00136] The imide may be preferably selected from 2-methyl-glutarimide, 3-methyl- glutarimide, 2-ethyl-glutarimide, 3-ethyl-glutarimide, 2-methyl-succinimide and 2-ethyl-succinimide.

[00137] For example, in order to obtain a compound of formula (la) or (lb) wherein

R² respectively R5 is Ch -, then the imide can be a cyclic imide of formula

[00139] The amine is preferably a primary amine of general formula R¹'-NH2, with R defined as above.

[00140] The reaction for preparing the viscosifier may be performed for example, at a temperature ranging from 20°C to 200°C, preferably from 50°C to 180°C, more preferably from 100°C to 160°C. In the case of lighter amines, such as amines having less than 6 carbon atoms, the reaction may be performed with a progressive heating in order to avoid loss of amines through evaporation or may be performed under pressure to keep the amine in the liquid phase. For example, at the beginning of the reaction, the temperature of the mixture (ingredients) is approximately equal to the boiling point of the amine.

[00141] The reaction for preparing the viscosifier is preferably performed under atmospheric pressure.

[00142] The viscosifier used as component c) in the formulations according to the invention may be a mixture (S) comprising the N-hydrocarbyldiamides (I) or (la) and (lb) and at least one solvent, said compound of formula (I) respectively the composition comprising (la) and (lb) being partially or fully solubilized in said solvent.

[00143] In such mixtures (S), the N-hydrocarbyldiamide compounds (I) or (la) and (lb) are preferably fully solubilized in the at least one solvent. The mixture (S) is preferably a solution comprising at least one solvent and, fully dissolved therein, at least one compound of formula (I) or the compounds of formula (la) and (lb), that is to say the mixture (S) is free of any compound that would be insolubilized in the solvent.

[00144] Preferably, the mixture (S) is one which, when at room temperature and at atmospheric pressure (20 °C, 1 atm), comprises the N- hydrocarbyldiamides (I) or (la) and (lb) in partially or fully solubilized form in the solvent. More preferably, the mixture (S) is one which, when at room temperature and at atmospheric pressure, comprises the N- hydrocarbyldiamides of formula (I) or the mixture of (la) and (lb) in fully solubilized form.

[00145] Advantageously, the mixture (S) is one which, when at 60°C and at

atmospheric pressure, comprises the N-hydrocarbyldiamides (I) or (la) and (lb) in fully solubilized form in the solvent. Preferably, the mixture (S) is one which, when at 40°C and at atmospheric pressure, comprises the N- hydrocarbyldiamides (I) or (la) and (lb) in fully solubilized form.

[00146] Advantageously, the mixture (S) is a solution when it is put at 60°C and at atmospheric pressure. Preferably, the mixture (S) is a solution when it is put at 40°C and at atmospheric pressure. More preferably, the mixture (S) is a solution when it is put at room temperature (20°C) and at atmospheric pressure.

[00147] According to an embodiment, the solvent used in the mixture (S) is a good solvent and can be a polar solvent or a mixture of a polar solvent and an apolar solvent. Within the meaning of the present invention, by "polar solvents", it is to be understood solvents having a polar and hydrogen bonding components respectively δ_ρ and 5h (Hansen solubility parameter) strictly greater than 0. Hansen solubility parameters are well known for the skilled person: δ_ρ corresponds to the energy from dipolar intermolecular forces between molecules and 5h corresponds to the energy from hydrogen bonds between molecules.

[00148] According to an embodiment of the invention, the solvent of the

mixture (S) is selected from alcohols having from 1 to 10 carbon atoms, preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol.

[00149] According to an embodiment of the invention, the solvent of the

mixture (S) is selected from acetal derivatives having from 2 to 12 carbon atoms, and is preferably selected from the Augeo® family of solvents (available from Solvay SA) such as Augeo® SL191 which is a racemic mixture (+/-)-2,2-dimethyl-4-hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol.

[00150] According to an embodiment of the invention, the solvent of the mixture (S) is itself a mixture of (i) alcohols having from 1 to 10 carbon atoms (preferably selected from methanol, ethanol, isopropanol, butanol, isobutanol, diethylene glycol, butylene glycol, methyl propane diol), (ii) alkyl esters having from 2 to 12 carbon atoms (preferably selected from ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, ethylhexyl acetate or octyl acetate) and (iii) acetal derivatives having from 2 to 12 carbon atoms (preferably selected from the Solvay available Augeo family of solvents (available from Solvay SA such as Augeo® SL191 which is a racemic mixture (+/-)-2,2-dimethyl-4-hydroxymethyl-1 ,3-dioxolane also known as isopropylidene glycerol). [00151] According to an embodiment of the invention, the solvent of the mixture (S) is selected from lactate esters, in particular selected from methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 2-ethylhexyl lactate, especially from methyl L-lactate, ethyl L-lactate, n-propyl L-lactate, n-butyl L-lactate, 2-ethylhexyl L-lactate.

[00152] The mixture (S) may be from a liquid state to a flowable thick paste at temperatures ranging from 20°C to 50°C.

[00153] According to an embodiment of the invention, the N-hydrocarbyldiamide compound I respectively the mixture of N-hydrocarbyldiamines of formula (la) and (lb) in accordance with a preferred embodiment represents from 1 % to 75% by weight, preferably from 10% to 50% by weight, more preferably from 15% to 30% by weight, of the total weight of the mixture (S).

[00154] According to a particular embodiment, the mixture (S) of the invention comprises an N-hydrocarbyldiamide composition where in compounds (la) and (lb), R¹ and R⁴ differ in chain length. When the mixture (S) of the invention comprises such combination, the use of the mixture (S) is more flexible and can be used in very different carriers in order to allow the gelification of said carriers.

[00155] The mixture (S) according to the invention may be obtained by simple mixing of the ingredients (N-hydrocarbyldiamide compounds and solvent), preferably at a temperature comprised between 10°C and 60°C, ideally about 25°C (room temperature).

[00156] The formulations according to the invention comprise as component d) at least one biologically active ingredient, preferably a pharmaceutically active ingredient or an agriculturally active ingredient.

[00157] The term "biologically active ingredient", when used herein, is intended to denote an entity which interacts with biological material in a manner that dieseases in animals, such as mammals, may be prevented or combatted or which influences growth of agricultural crops or which combats weeds, insects, bacteria or fungi in agricultural crops. The animal, in particular the mammal, can be a human being. Alternatively, the animal can be any animal other than a human being. [00158] In accordance with a preferred embodiment, the formulation comprises an agriculturally active ingredient selected from the group consisiting of agriculturally active ingredient is selected from herbicides, insecticides, fungicides, parasiticides, plant growth regulators, fertilizers, bactericides and insect repellents.

[00159] Biologically active ingredients have been described in the literature in

great variety and the skilled person will select the appropriate active ingredient based on his professional knowledge and taking into account the individual case of application. No further details need to be given here.

[00160] There is no principal limitation as to the nature of the biologically active ingredient in the formulation of the present invention.

[00161] For the purpose of the invention the biologically active compounds are preferably biologically active compounds used to control agricultural pests and include, for example, herbicides, plant growth regulators, crop dessicants, fungicides, bacteriocides, bacteriostats, insecticides, and insect repellants.

[00162] Naturally, the formulation according to the invention may further contain any additive usually contemplated in phytosanitary formulations like for example safeners.

[00163] APPLICATIONS

[00164] The preferred application for the formulations according to the invention are agricultural formulations, for which now certain advantages which may be achieved are described in more detail.

[00165] The formulations according to the invention allow to achieve stabilized oil dispersions or emulsions with a great diversity of salts and/or active materials, in particular active compounds used to control agricultural pests. However, these concentrate formulations may also be convenient for vehiculing other active materials like fertilizers. These active materials and/or salts may be of very different chemical nature, like for example organic, inorganic, liposoluble or not.

[00166] The concentrate formulations may be highlighted in many ways. [00167] Firstly, they may be used as final oil dispersions that are directly prepared by the farm operators by dilution of the concentrates with water and optionally by addition of some additives.

[00168] Moreover, they may be used by industrial firms as vehicles for a plurality of agricultural, e.g. pesticidal active materials.

[00169] Thus, the farm operators may prepare pulverizable liquid compositions and in particular aqueous emulsions or suspoemulsions by diluting a concentrate according to the invention. Generally, they just proceed to a dilution with water and oil if necessary, and optionally also supplement the so-obtained pulverizable formulation with at least one ingredient chosen from salts, hydrocolloids and their mixtures. Of course, it is also possible for a concentrate formulation according to the invention to already contain such a material.

[00170] More particularly, the salts may be chosen among sodium carbonate,

sodium bicarbonate, ammonium sulfate and their mixtures.

[00171] As hydrocolloid particularly convenient for the invention, may be cited the guar.

[00172] Thus, a formulation according to the invention may be used by the farm operators for preparing different pulverizable compositions which may be kept for a long time without any undesirable phenomenon of demixtion.

[00173] The non-aqueous formulations supplemented with at least one ingredient chosen from salts like sodium carbonate, sodium bicarbonate, ammonium sulfate or their mixtures; hydrocolloids such as guar; and their mixtures as well as the corresponding emulsions obtained by a dilution of the concentrates into water, are also known under the name of tankmix.

[00174] A tankmix may be obtained by adding to a formulation according to the invention prepared as above mentioned, at least an ingredient chosen from salts, hydrocolloids and their mixtures to a homogenizer. The so obtained composition is then blended and diluted or not with water to form an emulsion.

[00175] Thus, according to a specific embodiment a tankmix according to the

invention contains less than 2 % by weight of water and preferably is anhydrous. [00176] Tankmix formulations according to the invention are pourable, show a good storage stability, are emulsifiable and provide stable emulsions when diluted into water.

[00177] The formulation according to the invention is also particularly interesting for industrial firms which, by using only one concentrate, may prepare a great diversity of pesticidal oil dispersions.

[00178] In particular, a pesticidal oil dispersion according to the invention may contain until 50 % in particular from 1 to 20 %, more preferably 3 to 10 % by weight of solid pesticidal active material(s) with respect to its total weight.

[00179] The particle size of such active materials preferably is lower than 50 μηη in particular lower than 20 μηη and more particularly lower than 10 μηη. This size may be measured by laser diffraction (CIPAC MT 187) or rough estimation of average diameter by optical microscopy.

[00180] Preferred agriculturally active materials for use in the formulationms

according to theinvention are abamectin, azamethiphos, azoxystrobin, cyproconazole, bordeaux mixture, carbendazim, chlorsulfuron, copper hydroxide, copper oxide, copper oxychloride, cymoxanil, diflubenzuron, PMP, ethofumesate, DMP, lenacil, fenoxaprop-p-ethyl, iodosulfuron, florasulam, flutriafol, imidacloprid, imidacloprid, b-cyfluthrin, indoxacarb, iprodione, isoproturon, mancozeb, copper oxy, metamitron, nicosulfuron, rimsulfuron, thiacloprid, deltamethrin, thiobendazole, uniconazole, difenconazole, oxyfluorfen, quizalofop-p-ethyl, tebuconazole and their mixtures.

[00181] It has to be noticed that the formulations according to the invention keep their storage stability when containing the active materials.

[00182] Pesticidal oil dispersions obtained with the formulations according to the inventions are still pourable. In particular, they preferably have a viscosity ranging from 500 to 3000 mPas.

[00183] A formulation according to the invention may be obtained by adding, in the order listed, a non-esterified vegetable oil as organic liquid, a viscosifier as defined in the claims, a surfactant and an active ingredient according to the invention to a homogenizer, and blending the compositions after each addition.

[00184] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[00185] (EXAMPLES

[00186] Example 1

[00187] Preparation of a N-hexyldiamide compound (also named hereafter C6 gelator 65/35)

[00188] C6 Gelator lsomer4/lsomer2 Ratio 65/35

[00189] In a 500 ml glass reactor equipped with a cooling system, 100.0 g of

methyl glutarimide (MGI) and 76.6 g of hexylamine and then 1.0 g of tBuONa was added. The reactor was then heated to 130°C and

maintained at the reaction temperature for 2.5h. Then the reaction mixture was cooled down. The solid was added into 400 ml of methylethylketone (MEK) and heated to 100°C. The solution was then cooled down and the obtained solid was collected by filtration and washed with ethyl acetate (EA , 2^*300ml). The obtained solid was dried in vacuo to give 137.0 g of white solid, the yield was 76%, the purity was >98%.

[00190] NMR analysis showed that the product was a mixture of 2 isomers:

- N -hexyl-4-methylpentanediamide (65 wt%),

- N¹-hexyl-2-methylpentanediamide (35 wt%).

[00191] All formulations were prepared in 8 to 20ml scintillation glass vials.

Appropriate weights of the gelator powder and the oils or solvents were weighted on a microbalance. Total weights of gelators plus liquid oil or solvent were from 3 to 18g.

[00192] Good dispersions and solubilizations of the gelators at high temperatures (90°C to 1 10°C) were obtained using a tip sonicator (Branson Sonifier® 450) 6.3 mm diameter tip at a duty cycle set at 50%, power at 70%, with sonication durations set at 4 minutes. All samples were fluid, transparent and clear at end of the sonicating preparation. [00193] Unless specifically mentioned otherwise all samples were left to cool back to room temperature on a bench. The qualitative visual verification of the gelation was done by simply upturning the vials. The gelation was considered successful if no flow was observed upon inverting the vial at room temperature.

[00194] (Example 2

[00195] Pesticidal compositions in Rapeseed Oil

[00196] A composition 1 was prepared with Rapeseed oil RADIA 6105 from Oleon, 0.75 wt% of the C6 gelator (65/35) from example 1 and 30wt% of the nonionic surfactant Alkamuls VO 2003 from Solvay. A formulation was obtained by adding 4 wt% of Nicosulfuron in composition 1. The obtained pesticidal formulation was stable against sedimentation and presented no or very little syneresis upon storage at 45°C. The sample displayed good shear thinning behavior when subjected to a steady shear in a rheometer compatible with an easy pour from a container when shaken.

[00197] Upon injection in water with a 50 times or more dilution ratio good

immediate "blooming" self-emu Isification is observed.

[00198] [Example 3

[00199] Pesticidal compositions in methylated rapeseed oil

[00200] A composition 2 was prepared with methylated Rapeseed oil RADIA 7956 from Oleon, 0.75wt% of the C6 gelator (65/35) from example 1 and 30wt% of the nonionic surfactant Alkamuls T85V from Solvay. A formulation was obtained by adding 4 wt% of Nicosulfuron to composition 2. The obtained pesticidal formulation was stable against sedimentation and presented no or very little syneresis upon storage at 45°C. The sample displayed good shear thinning behavior when subjected to a steady shear in a rheometer compatible with an easy pour from a container when shaken.

[00201] Upon injection in water with a 50 times or more dilution ratio good

immediate "blooming" self-emu Isification was observed.

[00202] [Example 4

[00203] A mixture S was prepared by weighing the C6 gelator (65/35) from

example 1 in n-Propyl L-lactate (Purasolv NPL from Corbion) to obtain a 25wt% solution and placing it in an oven at 60°C for complete dissolution. [00204] For the following examples all performance tests were performed as follows:

[00205] Blooming tests were conducted according to the Cipac MT36.3 method listed in the CIPAC (Collaborative International Pesticide Analytical Council Guide lines) published in the CIPAC Handbook J 2000 on a ¼ reduced scale and all measurements were conducted diluting 2% in volume of the Oil Dispersion into 98% CIPAC D water at 30°C, after 10 inversions, the test tubes were maintained in a 30°C oven. Observations were made after 2hours using digital cameras image capture and image treatment to quantify creaming and sedimentation.

[00206] Viscosity measurements were made using a Gilson Viscoman.

[00207] Stability measurements were conducted by placing the formulations in a 40°C oven and capturing the image of each formulation after the storage time at 40°C indicated in each example.

[00208] (Example 5

[00209] Pesticidal compositions in rapeseed oil

[00210] A composition A1 was prepared in Rapeseed oil RADIA 6105 from Oleon and adding Mesotrione powder, the nonionic surfactant Alkamuls VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A1 to form the formulation B1. The formulation B1 is as follows: Mesotrione (1 OOg/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n-Propyl L-lactate 1.95w% the rest being rapeseed oil. After a hand mixing at room temperature, the formulation B1 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[0021 1] The results of performance tests are the following:

Blooming: 1.7 % Creaming and 0.5 % Sedimentation

Viscosity: 300-500cps

Stability: No Syneresis after 8 Weeks at 40°C [00212] [Example 6

[00213] Pesticidal compositions in methylated rapeseed oil

[00214] A composition A2 was prepared in methylated Rapeseed oil RADIA 7956 from Oleon and adding Mesotrione powder, the nonionic Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A2 to form the formulation B2. The formulation B2 is as follows: Mesotrione (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.2wt%, n-Propyl L-lactate 3.6w% the rest being methylated rapeseed oil. After a hand mixing at room

temperature, the formulation B2 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00215] The results of performance tests are the following:

Blooming: 1.8% creaming and 0.3% Sedimentation

Viscosity: 300-500cps

Stability: 7% Syneresis after 8weeks at 40°C

[00216] (Example 7

[00217] Pesticidal compositions in Soy Bean oil

[00218] A composition A3 was prepared in Soy Bean Oil Amesolv SOR Soybean oil from Ametech and adding Mesotrione powder, the nonionic surfactant Alkamuls VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A3 to form the formulation B3. The formulation B3 is as follows:

Mesotrione (100g/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n- Propyl L-lactate 1.95w% the rest being Soy Bean oil. After a hand mixing at room temperature, the formulation B3 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00219] The results of performance tests are the following:

Blooming: 2.58% Creaming 0.58% Sedimentation

Viscosity: 300-500 cps

Stability: No Syneresis after 8 weeks at 40°C [00220] (Example 8

[00221 ] Pesticidal compositions in Methyl Soyate/

[00222] A composition A4 was prepared in Methyl Soyate Amesolv MTES from

Ametch and adding Mesotrione powder, the nonionic surfactant Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A4 to form the formulation B4. The formulation B4 is as follows: Mesotrione (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.2wt%, n-Propyl L-lactate 3.6w% the rest being Methyl Soyate. After a hand mixing at room temperature, the formulation B4 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00223] The results of performance tests are the following:

Blooming: 1.2% Creaming 0.3% Sedimentation

Viscosity: 300-500 cps

Stability: 8% Syneresis after 8 weeks at 40°C

[00224] (Example 9

[00225] Pesticidal compositions in rapeseed oil

[00226] A composition A5 was prepared in Rapeseed oil RADIA 6105 from Oleon and adding Nicosulfuron powder, the nonionic surfactant Alkamuls

VO2003 from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N- 5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A5 to form the formulation B5. The formulation B5 is as follows: Nicosulfuron (100g/l), Alkamuls VO 2003 7wt%, C6 Gelator 0.65wt%, n-Propyl L-lactate 1.95w% the rest being rapeseed oil. After a hand mixing at room temperature, the formulation B5 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00227] The results of performance tests are the following:

Blooming: 2.1 % Creaming 0.5% Sedimentation

Viscosity: < 800 cps

Stability: No Syneresis after 8weeks at 40°C [00228] (Example 10

[00229] Pesticidal compositions in methylated rapeseed oil

[00230] A composition A6 was prepared in methylated Rapeseed oil RADIA 7956 from Oleon and adding Nicosulfuron powder, the nonionic Alkamuls T85V from Solvay wet grinding it with Ultraturrax (IKA T10 Basic S10N-5G medium speed) for 1.5 minutes. The mixture S from example 4 previously heated to 60°C is then introduced to the composition A6 to form the formulation B6. The formulation B6 is as follows: Nicosulfuron (1 OOg/l), Alkamuls T85V 7wt%, C6 Gelator 1.5wt%, n-Propyl L-lactate 4.5w% the rest being methylated rapeseed oil. After a hand mixing at room temperature, the formulation B6 is left at rest until gel formation. The flowable formulation is obtained using vortex mixing with glass beads.

[00231] The results of performance tests are the following:

Blooming: 0.9% creaming 0.4%sedimentation

Viscosity: 300-500 cps

Stability: 7% Syneresis after 8 weeks at 40°C.

Claims

C L A I M S

1. A non-aqueous, emulsifiable formulation comprising

a) at least 3 % by weight of at least one surfactant,

b) at least 10 % by weight of an organic liquid,

c) at least 0.1 % by weight of at least one viscosifier selected from N- hydrocarbyldiamides of general formula (I)

wherein

R^a or R^b is selected from hydrogen or a linear, branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms, with the proviso that either R^a or R^b is hydrogen,

R^c is selected from cyclic or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 2 to 25 carbon atoms

and

d) at least 0.5wt% of at least one biologically active ingredient.

The formulation of claim 1 wherein the viscosifier c) is a N- hydrocarbyldiamide composition comprising

c1 ) a compound of formula (la)

wherein

R is a linear or branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms,

R² is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 1 to 15 carbon atoms, and

R³ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms, and

c2) a compound of formula (lb)

wherein

R is a linear or branched or cyclic, saturated or unsaturated, hydrocarbon chain having from 1 to 40 carbon atoms,

R² is selected from linear or branched, saturated or unsaturated, hydrocarbon aliphatic chain having from 1 to 15 carbon atoms, and

R³ is selected from linear or branched alkyl groups with 1 to 8 carbon atoms.

3. The formulation of claim 1 or 2 wherein the surfactant is selected from

the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants or alkoxylated derivatives of anionic surfactants, cationic surfactants or amphoteric surfactants.

4. The formulation of any of claims 1 to 3 wherein the viscosifier comprises a mixture of at least one N-hydrocarbyldiamide of formula (I) as defined in claim 1 and at least one solvent or a N-hydrocarbylamide composition comprising compounds of formula (la) and (lb) as defined in claim 2, and at least one solvent, said N-hydrocarbyldiamide of formula (I) respectively N- hydrocarbylamide composition comprising compounds of formula (la) and (lb) being partially or fully solubilized in said solvent, preferably being fully solubilized in said solvent.

5. The formulation of any of claims 1 to 4 wherein the surfactant comprises at least two C2-C10 oxyalkylene moieties and is free of any components containing one or more aromatic rings.

6. The formulation of any of claims 1 to 5 wherein the surfactant is selected from polyalkylene glycol esters of fatty acids.

7. The formulation of any of claims 1 to 6 wherein the organic liquid is selected from esterified or non esterified mineral oils, vegetable oils, animal oils or synthetic oils.

8. The formulation of any of claims 1 to 7 wherein components (a) and (b) are present in a weight ratio (a) to (b) ranging from 0.1 to 4, preferably from 0.25 to 1.25.

9. The formulation of any of claims 1 to 8 comprising 10 to 60 wt% of

component a) 10 to 90 wt% of component b) and 0.25 to 5 wt% of component c), each wt% value being based on the total weight of the formulation.

10. The formulation of any of claims 1 to 9 wherein the biologically active

ingredient is selected from pharmaceutically active ingredients and agriculturally active ingredients.

1 1. The formulation of claim 10 wherein the agriculturally active ingredient is selected from herbicides, insecticides, fungicides, parasiticides, plant growth regulators, fertilizers, bactericides and insect repellents.

12. The formulation of any of claims 1 to 1 1 which comprises of from 1 to

20 wt%, based on the total weight of the formulation, of the biologically active ingredient.

13. Use of the formulation in accordance with any of claims 1 to 12 as

pharmaceutical or agricultural compositions.

14. A method for preventing or combatting diseases in animals, such as

mammals, or for preventing or combatting infestation of plants by pests and/or of regulating plant growth comprising the application a mixture obtained by diluting a formulation in accordance with any of claims 1 to 10 with water.