WO2015114590A1

WO2015114590A1 - Liquid non-aqueous pesticide composition, method for preparing the liquid non-aqueous pesticide composition and method for eliminating insects, acarids and nematodes in cultures

Info

Publication number: WO2015114590A1
Application number: PCT/IB2015/050732
Authority: WO
Inventors: Walter Luis Crivelli BOGGIANI
Original assignee: Pacific Agrosciencies S.A.I.C.; ZAMATARO, Carlos Eduardo De Oliveira
Priority date: 2014-02-03
Filing date: 2015-01-30
Publication date: 2015-08-06
Also published as: AR099451A1; BR102015002279A2; UY35974A

Abstract

The invention relates to a liquid non-aqueous pesticide composition, to a method for preparing the liquid non-aqueous pesticide composition and to a method for eliminating insects, acarids and nematodes in cultures, namely a liquid non-aqueous composition containing a concentrated pesticide, including an organic pesticide that is hardly soluble or insoluble in water, and which when diluted in water before its application (application liquor), generates a nanoparticle population that improves the bio-effectiveness of the pesticide. The formulation is useful for controlling a wide range of pests, including insects, acarids and nematodes in soy, wheat, maize, cotton, sunflower and horticultural product cultures in general. The composition comprises at least one organic pesticide that is hardly soluble or insoluble in water; a balanced mixture of non-ionic surfactants; one or more polar aprotic organic solvents; a non-water-miscible co-solvent; an anti-foaming agent and a stabiliser.

Description

NON-Aqueous LIQUID COMPOSITION, PROCEDURE FOR PREPARING NON-Aqueous LIQUID COMPOSITION AND METHOD FOR CLEARING INSECTS, MITES AND NEMATODES

FIELD OF INVENTION

The present invention relates to a liquid composition of a concentrated pesticide comprising at least one organic pesticide compound which is poorly soluble or insoluble in water and which, when diluted with water for application (broth), It generates a stable nanoparticle population that improves the bio-efficacy of the pesticide.

BACKGROUND OF THE INVENTION

State-of-the-art pesticide formulations range from formulations that give true solutions with water-soluble active ingredients to classic emulsions from water-insoluble active ingredients.

The insecticides of the chemical family of macrocyclic lactones, namely Avermectins, one of two large families, according to the origin of the fermentation organism (Avermectins and Milbemycin), are poorly soluble in water. These insecticides are insoluble or practically insoluble and generate, when applied directly to water, very unstable aqueous compositions.

Their water solubility is less than 1 g / lt at 25 ° C, 1013 mbar. In the case of Abamectin it is 7 to 10μ9 / Ι at 20 ° C and in the case of Emamectin Benzoate it is 0.024 g / lt at 25 ° C, pH = 7. By incorporating said active ingredients into water in direct form, when diluted in 0.5% water, or even in the concentrations of commonly used application broths, a small part solubilizes and the remainder remains in insoluble form. if not a stable composition. When this occurs, the development employs formulations WP (wettable powder), SC (water-based concentrated suspension), EC (emulsifiable concentrate), EW (oil-in-water emulsion, water in continuous phase), WG (dispersible granules), among others, less frequent. Analyzing the disadvantages of the above, in the case of WP powders, is found physicochemical stability in the formulation itself, particle sizes found in mills in general are smaller than 40 μιη, in the best case sizes ranging from 5 to 15 μηι (with special mills and with high production cost can be improved but not usual), and it is difficult to stabilize aqueous suspension, once diluted with water for application. In the case of SC, the active principle is finely divided into suspension and the particle sizes found with wet milling must be less than 20 μιη, often the sizes can reach 4 μιη, and sometimes, with elaborate techniques, reach a range between 1 and 4μιη; On the other hand, the formulation itself is a metastable system. It is very common to find formulations WP (Wettable Powder), WG (Dispersible Granules), SC (Concentrated Suspension), which due to the intrinsic characteristics clog up the inputs of the application machines, thus compromising bio-efficacy.

In the case of EC, the active ingredient is dissolved in a non-water miscible solvent (usual solubility less than 0.1 g / lt), with emulsifiers, so that when diluted in water they form Type O emulsions. / W; In general, stability in formulation is obtained, and particle sizes in broths are very varied and smaller than 100 μιη, sometimes it is difficult to miniemulsify, reaching sizes between 0.5 and 2 μιη. It is difficult to stabilize a miniemulsion in the broth at a certain time, but also begins to compromise the bioefficacy, among other disadvantages such as being high toxicity solvents, etc.

In the case of EW, the active or water-insoluble principle is emulsified, the phase being water; The formulation itself is a metastable system that is difficult to stabilize, particle sizes depend greatly on agitation, lose overall stability when diluted in water, and no advances in particle diameter reduction and time support are also achieved. . Another slightly more complex possibility is ME microemulsion, the active principle being microemulsion in a continuous phase water, obtaining here nanometric sizes ranging from 10 to 200 nm, which form spontaneously, being translucent to slightly opalescent in appearance. and, when diluted in water for their application, can generate classic microemulsions or emulsions, depending on multiple factors: formed microstructures are guided by changes in intensive system variations (temperature, dispersed phase volumetric fraction, chemical potential); ME is known to be stable in a limited range of temperatures; It is also known that the formation of EM is complex, depending on multiple factors such as surfactant / active ingredient ratio, type of cosolvent, etc., hence it can form with proven EM stability of assets ranging up to 25% active ingredient. Higher concentrations tend to be unstable, with small temperature changes, especially when additives, antioxidants need to be incorporated. Lastly, although less frequently, nanoemulsions such as O / W, such as O / W, which have particle sizes ranging from 20 to 500 nm, which are not thermodynamically stable, can be developed as a water-diluting formulation. they must be given considerable energy to manufacture, being metastable opaque liquids, difficult to sustain over the life of the product and tending to destabilize.

It means that for the EW, SC formulations, O / W nanoemulsions are metastable, and phenomena occur that destabilize them, even though they have high kinetic stability. In the case of nanoemulsions with particle sizes smaller than 500 nm, the thermal agitation (brownian motion) is greater than the sedimentation velocity produced by gravity; In this sense, the sedimentation mechanism does not influence much as a negative force, being the most important mechanism in the destabilization of Ostwald maturation, which consists in the growth of larger drops at the expense of the smaller ones (this also occurs in EW, SE). In SC, the main negative mechanism is the sedimentation phenomenon regulated by Stokes law, with other factors such as flocculation and coalescence. Therefore, in order to avoid all these disadvantages, it is an object of the present invention to provide a stable liquid formulation throughout the life of the product, in the form of MEC (Microemulsifiable Concentrate), which once diluted with water for its application, be easily microemulsified, and form an aqueous composition of the active ingredient stable for a certain period of time, giving nanoparticles as the ME must have; thereby obtaining translucent to slightly opalescent aqueous dilutions without forming thick material (crystals, various precipitated particles) and yielding particles from 10 to 500 nm.

[0008] Another objective is to provide a stable and concentrated formulation of the active ingredient, which may reach a concentration of up to 40% w / w active, with the resulting improvements, such as the lower application dose. / ha, adequate costs, lower inventory volumes, etc.

It is also an object of the present invention to provide the application broth with a population of nanoparticles which will yield improvements in bioefficiency compared to commercially available formulations.

TECHNICAL STATE

Document BRPI0307834-5, filed on 02/10/2003, relating to SYNERGISTIC INSECTICIDES MIXTURES, which describes the use of abamectin or its components of the same group that make up a basic formulation, is known from the prior art. second components, and therefore the active principle is distinct from that foreseen in the present patent application.

Document BRPI 0516706-2, filed 10/31/2005, on INSECTICIDE COMPOSITION AND METHOD FOR CONTROLING INSECTS, describes at least one fulminant action insecticide compound selected from group (A) comprising imidadpride, acetamipride .. abamectin, emamectin, emamectin benzoate among others and at least one long-term effective insecticidal compound selected from the group (B) of insect growth regulators comprising benzophenyl urea (BPU) compounds selected from novaluron, lufenuron, hexaflumuron, among others. This composition is distinct from that employed in the present application, which comprises at least one poorly soluble or water-insoluble organic pesticide in a concentration of 4.0 to 40% w / w; a balanced mixture of nonionic surfactants at a concentration of 1 to 95% w / w; a polar aprotic organic solvent or more than one at a concentration of 5 to 75% w / w, a non-water miscible cosolvent at a concentration of 0 to 30% w / w, a defoamer at a concentration of 0 to 2% w / w / eg a stabilizer at a concentration of 0 to 1% w / w. Document BRPI102013028849-7, filed on 08/1 1/2013, with unionist priority JP2012-248099, of 12/1 1/2012, concerning AGROCHEMICAL COMPOSITION AND PLANT GROWTH PROMOTION METHOD, describes a pesticide composition with a compound represented by the formula with at least one active insecticidal compound of group (A): imidadoprid, dotianidine, thiametoxan, acetamiprid, thiadoprid ... abamectin, emamectin, among other macrocyclics. In this formulation the active compound based on abamectin and others enters as a second component, generating a formula distinct from that presented in the present patent application, which is a combination of components according to the formulation: at least one sparingly soluble or insoluble organic pesticide. water at a concentration of 4.0 to 40% w / w; a balanced mixture of nonionic surfactants at a concentration of 1 to 95% w / w; a polar aprotic organic solvent or more than one at a concentration of 5 to 75% w / w, a non-water miscible cosolvent at a concentration of 0 to 30% w / w, a defoamer at a concentration of 0 to 2% w / w / eg a stabilizer at a concentration of 0 to 1% w / w.

[0013] Document BRPI1001224-9, filed on April 7, 2010, on the INJECTABLE FORMULATION MANUFACTURING PROCESS, THE FLUAZURON BASED ASSOCIATION WITH AVERMECTINES FOR THE CONTROL AND PREVENTION OF NAME AND ECTOPARASITES IN DOMESTIC ANIMALS avermectins and other solvent components such as: 2-pyrrolidone, N-methylpyrrolidone, benzyl benzoate; fixed oils: sesame oil, cottonseed oil, soybean oil, corn oil, coconut oil, carnauba oil, castor oil and olive oil; preservatives and stabilizers; The active ingredient being the active ingredient being fluazuron with a concentration of 1 to 20%. The active ingredients of this formulation are distinct from those employed in the formulation of the present invention.

[0014] Document BRPI0502944-9, filed on 07/27/2005, concerning ENDECTOCIDA ASSOCIATED WITH DISABLED VIRUS, OAC TYPE, OBTAINED FROM CELL CULTURE, EMULSIFIED IN OIL SOLVENT FOR THE TREATMENT OF BOVINOS EVOSROS COMVOSTA ENDO AND ECTOPARASITES SENSITIVE TO FORMULATION COMPOUNDS, AS WELL AS IMMUNIZATION AGAINST AFTOSA FEVER describes a process consisting of the association of inactivated OAC-type viruses, obtained from cell cultures, emulsified in polymeric or oily solvent, with an endectocide, represented by the following active principles: ivermectin, abamectin, doramectin ... emamectin at concentrations from 0.1 to 90%. This formulation is different from that presented in the present patent application, and the purpose of this prior art formulation is distinct, as are the components and the means employed in obtaining it.

Document CN1442059, filed on 17/09/2003, concerning AEROSOL AVERMECTIN AND PREPARATION METHOD, describes a compound where the abamectin smoke agent is used to prevent and eliminate pests from agricultural crops, the formulation contains: 0.1 to 10% abamectin, 0.1 to 15% surfactant, 45 to 95% solvent and 1 to 30% co-solvent. This composition is distinct from that presented in the present patent application, notably because, in the proposal of this patent application, defined ionic surfactants are employed, in addition to the fact that the present invention employs different levels of concentration of the components, since it has been studied and studied. developed to obtain great effectiveness within its propositions, as will be attested in the studies that integrate this descriptive report.

Document CN1654446, filed 17/08/2005 on MEDICAL INSECT FERTILIZER AND ITS PRODUCTION METHOD describes a disturbance-free fertilizer for the prevention and killing of nematodes and other ground pests consisting of 1 to 4%. avermectin, 0.1 to 2 wt.% abamectin, 2 to 8 wt.% dodecyl benzene sulfonate sodium or potassium, and other components such as ammonium, for example, which make this composition distinct from that described in present patent application, both qualitatively and quantitatively.

JPH07173017, filed 11/01/07 1995, reports a COMPOSITION FOR THE PREVENTION AGAINST PINK DEATH AND THEIR PREPARATION METHOD, which describes a composition containing avermectin as an active ingredient and capable of manifesting strong activities against Bursaphelenchus xylophilos and / or Monochamus alternatus. In the composition, abamectin and ivermectin are especially suitable as the avermectin-based compound. The composition is obtained by dissolving the avermectin-base compound and a nonionic surfactant in a water miscible solvent and then adding water thereto. The resulting composition is improved with the solubility of the active ingredient in water, having excellent dispersibility in the tree body. Polyoxyiteline hardened castor oil, polyoxyethylene alkyl ethers, polyoxypropylene, etc. are cited as the nonionic surfactant. Although this formulation reports some components employed in the formulation of the present patent application, it does not report the association of the invention, in qualitative and quantitative terms, which besides making it different, involves the fundamental characteristics to obtain the technical effect advocated. invention and recorded in the tests accompanying this descriptive report.

Document RU2156054, filed September 20, 2000, concerning Enhanced Insecticide Preparation, describes a complex of avermectins such as avertin N as an antiparasitic agent of Streptomyces avermetilis mycelium VKPM S - 1440, with increased group B content. (67.8 to 77.4%) and to a similar extent other drug avermectin complexes may also be used as aversectin C, or abamectin, ivermectin or other avermectin-based active substances. This composition uses only one of the components of the formulation of the present patent application, being totally distinct in both qualitative and quantitative terms.

Document CN101223881, filed July 23, 2008, concerning ABAMECTIN or BANLEPTN MIXED ACIDARIC DISINFECTION COMPOUNDS, describes a composition of chitin and emamectin benzoate, wherein the dosage form of the preparation is characterized in that it is The microemulsion form and the percentage by weight of the components effective in the preparation of the compound contain 0.5 to 10% chitin, 0.2 to 2% avermectin, or 0.2 to 1.5% emamectin benzoate with rest of an auxiliary agent, a cosolvent and water. This formulation is different in qualitative and quantitative terms from the patent application in question. The use of a cosolvent is common not only In this formulation of the state of the art, as well as in others, such fact alone does not compromise the inventive act of the present patent application, when associated with the use of abamectin and other compounds of its group.

Document CN101366387, filed 18/02/2009, concerning AGRICULTURAL CHEMICAL COMPOSITION, describes a pesticidal composition comprising avermectin with the effective amount of methyl abamectin benzoate and synergistic, wherein the preferred weight ratio of avermectin to methyl abamectin benzoate is between 20 to 1 and 1 to 10. The preferred weight product is between 10 to 1 and 1 to 5, and the most preferred weight ratio is between 2 to 1 and 1 to 2. The composition is also qualitatively and quantitatively different from that disclosed in the present patent application.

SUMMARY OF THE INVENTION

The present invention provides a liquid composition of a concentrated pesticide, in the form of a microemulsifiable concentrate, stable throughout the life of the product, comprising at least one organic pesticide that is poorly soluble or even insoluble in water, and which when diluted with water for application (application broth) generates translucent to slightly opalescent aqueous dilutions of a 10 to 500 nm population of nanoparticles, stable all the time, for a minimum of 12 ha from their formation, up to and including to be stable for 24 hours after its formation.

The pesticide is selected from the group of macrocyclic lactone insecticides, namely Avermectins and more preferably from Abamectin and Emamectin Benzoate. Pesticide concentrations range from 4 to 40% w / w.

The formulation is useful for the control of a wide range of pests, including: insects, mites and nematodes in soybean, wheat, corn, cotton, sunflower and horticultural crops in general.

[0024] The present formulation improves the bio-efficacy of the pesticide, requiring a lower application rate / ha, the costs are more appropriate, and working with lower stock volumes, etc.

DESCRIPTION OF THE FIGURES The following figure is presented, without limitation, on the inventive scope of this patent application:

FIG. 1: Flow with the origin and classification of macrocyclic lactones: avermectins and milbemicines (Taken from Lifscllitz et al 2002). Origin and classification of macrocyclic lactones: avermectins and milbemicines {Lifschltz et al 2002).

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a liquid composition of a concentrated pesticide comprising at least one organic pesticide which is poorly soluble or even insoluble in water and which when diluted with water for application (application broth) generates a nanoparticle population.

[0027] The formulation is a stable, non-aqueous base solution in which the active ingredient is fully dissolved to form a true solution which upon dilution with water forms a stable microemulsion for at least 12 h for application. which differentiates it from SL formulations (which give true solutions when diluted in water but the active principle must be water soluble) and EC (which form classic emulsions when diluted in water) from water-insoluble active principles. , form in the nanoparticle broth in a microemulsion system. Although there is no terminology specified in FAO, it can be called MEC (microemulsifiable) formulation, forming nanoparticles when diluted in water.

The formation of the microemulsion in the broth has peculiar characteristics that make it attractive, such as being thermodynamically stable (no agitation and energy input), spontaneously formed, translucent and very slightly opalescent appearance, with diameter of particles from 10 to 200 nm.

The pesticide compound used is from the chemical family of macrocyclic lactones, namely Avermectins. Macrocyclic lactones belong to two large families, according to the origin of the fermentation organism (Avermectins and Milbemycin), and the structural chemical formula below shows Abamectin and Ivermectin:

Abamectin Invermectin

Source: Journal of the Brazilian Chemical Society

Avermectins are macrocyclic lactones of natural origin produced by the fungus Streptomyces avermitilis, with insecticidal, acaricidal and anthelmintic properties. In the family of Avermectins are Ivermectin, Selamectin, Doramectin and Abamectin.

The complex chemical structure of these drugs corresponds to a 16 (sixteen) membered macrocyclic lactone, similar to that of macrolide antibiotics (but without bacterial effect), unique to a benzofuran group (C2 to C8) and a spirochete ring (C17 to C25). These are large molecules with molecular weights between 600 kDa (milbemycin) and 800 kDa (avermectin) (Lifschitz et al 2002).

Within Avermectins there are active ingredients such as Doramectin, Eprinomectin, Ivermectin, Selamectin, which are for veterinary use only, a special case like Abamectin which is also used in Agrochemicals and Emamectin benzoate which is used only in Agrochemicals. Within Avermectins there are Abamectin and Alvermectin, very similar compounds that differ only in their chemical structure by the unsaturated double bond between carbons 22 and 23.

Specifically, the present invention encompasses the components of the Avermectin Family, working with the insecticide molecules used in crop protection, not forgetting that the other components of veterinary use are included in this study, and are applicable to the development .

More particularly, the present invention relates to formulations with Abamectin and Emamectin Benzoate. These insecticides are almost completely insoluble in water and generate very unstable aqueous formulations. Below is the structural formula of Abamectin:

up to 8tA-. O * Ha 0 <*

'8 ^* 8'. CH »G«

Abamectin is a derivative of compounds obtained by fermentation of soil bacteria Streptomyces avermitilis. It is a mixture of Avermectins containing more than 80% avermectin B1 a and the remainder of avermectin B1 b. These two compounds B1a and B1b have certain similar toxicological properties. Abamectin is an insecticide, acaricide and nematicide. It is used to control insects and mites that can be pests on plants and animals.

It is used in fruit, vegetable and ornamental crop cultivation; in homes, ant control and veterinary as anthelmintic.

Below is the structural formula of Emamectin:

Emamectin is the 4 "-Deoxy-4" -methylaminated derivative Abamectin. It is a 16 (sixteen) membered macrocyclic lactone produced by the fermentation of the soil fungus Streptomyces avermitilis. It is usually prepared as Emamectin Benzoate. Emamectin benzoate is widely used to control lepidopteran pests in agricultural products. With the low required use rate of the activol ingredient (~ 6 g / acre) and its broad spectrum of applicability as an insecticide it has gained significant popularity among farmers. It is a product in the systemic that has a mode of action based on the activation of chlorine channels, with rapid absorption by the plant and rapid degradation on its surface, which favors its compatibility with the auxiliary fauna. Lepidopteran pests are one of the most harmful to fruit and grape crops because they attack the most important plant organs and fruits, producing a direct decrease on crop yield.

They are also effective against pine wood nematodes (Bursaphelenchus xylophilus) and the eradication of fish lice.

Emamectin benzoate salt, in particular, is widely used as an insecticide and is approved by the EPA (Enviromental Protection Agency) for use in preventing emerald ash borer.

The present formulation is used in soybean, wheat, corn, cotton, sunflower and fruit crops in general against a wide range of pests, insects, mites and nematodes. Among the pests are cited, such as: Helicoverpa, Heliothis, Anticarsia, Spodoptera, etc.

It is particularly useful for the control of caterpillars and bed bugs (small black winged bugs, green bedbug, brown bedbug, field bedbug, alfalfa bedbug, etc.) in general.

It is a stable non-aqueous liquid formulation throughout the life of the product which, once diluted with water for application, forms an aqueous composition of the active ingredient, giving nanoparticles as MEs should have; translucent to slightly opalescent aqueous dilutions are obtained, without forming thick material (crystals, miscellaneous precipitated particles), giving particles of 10 to 500 nm, preferably less than 300 nm and better still less than 100 nm, stable all the time for a minimum period of 12 ha from its formation. Moreover, as stated above, when forming an ME by diluting water, it does not require agitation to be formed, only the minimum to incorporate it into the total water and homogenize; in this sense it will be an MEC formulation. In addition stability of the formulation is as specified by the FAO for cold stability for 7 days at 0 ° C (CIPAC MT 39.3) and cold stability for 7 days at 0 ° C (CIPAC MT 39.3) accelerated by heating for 14 (fourteen) days at 52 ° C (CIPAC MT 46.3), as well as the quality items (active ingredient dosing, etc.) should not be changed after storage.

[0044] The present formulation improves the bio-efficacy of the pesticide, requiring a lower application rate / ha, costs are more appropriate, and when working with lower stock volumes, etc.

The liquid, non-aqueous composition comprises:

1 - Avermectin group, macrocyclic lactone 4.0 to 40% w / w

2- A balanced mixture of 1 to 95% w / w nonionic surfactants

3 - An aprotic dipolar organic solvent or more than 5 to 75% w / w

4 - A non-water miscible cosolvent 0 to 30% w / w

5 - A defoamer 0 to 2% w / w

6 - Formulation stabilizer 0 to 1% w / w.

They may additionally contain preservatives, thickeners, colorants and other adjuvants of the formulation.

[0047] 1- The active ingredient is selected from the group belonging to the chemical family of Avermectins, which may be the active ingredient CAS No. 71751 -41-2, described in The Pesticide Manual 14 ed., 2005, p. 3 and 4; or the asset with CAS No. 137335 -79-6, its Benzoate salt with CAS No. 137512-74-4, described in The Pesticide Manual 14 ed., 2005, p. 385 e386.

Monograph Number: 0000002

Title: Abamectin

CAS Registration Number: 71751-41 -2

CAS Name: Avermectin B 1

Additional names: 5-0-demethyl avermectin A 1a and 5-0-demethyl-25-de (1-methylpropyl) -25- (1-methylethyljavermectin A 1 a (4: 1); avermectin B1a / b.

Monograph Number: 0003554

Title: Emamectin

CAS Registration Number: 137335-79-6; 121124-29-6 (major component); 121424-52-0 (minor component) Additional Names: (4 "R) -5-0-demethyl-4" -deoxy-4 "- (methylamino) avermectin

1a and (4 "R) -5-0-demethyl-25-de (1-methylpropy1) -4" -deoxy-4 "- (methy lamino) -

25- (1-methylethyl) avermectin A 1 to (9: 1).

Derived Type: Benzoate

CAS Registration Number: 137512-74-4

Additional Names: 4 "-Deoxy-4" -epi-N-methylamino avermectin 81 benzoate pKa: pKa 4.2; 7.6

Use: Insecticide.

[0048] 2- Perfectly balanced mixtures of nonionic surfactants are selected from two families, namely CAS No. 9016-45-9 and CAS No. 68131-39-5.

The mixture may range from 10 to 90% CAS No. 9016-45-9 and from 10 to 90% CAS No. 68131 -39-5.

More particularly, CAS No. 9016-45-9 and CAS No. 68131 -39-5, in a ratio of both of which may range from 20% CAS No. 9016-45-9 plus 80% CAS No. 68131 -39-5 to 80% CAS No 9016-45-9 plus 20% CAS No 68131 -39-5.

The CAS No. 68131-39-5 family belongs to the ethoxylated (C12 -C15) linear alkyl alcohols.

Ethoxylated fatty alcohols have general structure:

R 1 is -O - (CH 2 -CH 2 O) n -H.

In general commercial products have an R1 = C12 - C15 and a wide Poisson type distribution with n = 3 greater than 10, depending on these combinations the compounds will be more or less detergents, surfactants, dispersants of more or less less foam, etc.

There are several chemical families according to R1, either a straight or branched chain or a mixture of both, and establishing a particular CAS No., and within each family the compounds vary according to the number of carbons and structure in R1, and the distinct n of ethoxylation.

For CAS family 68131 -39-5, the ethoxylated (C12 -C15) linear alkyl alcohols R1 are a C12 to C15 alkyl straight chain (no branching), and with n = 0 to 9.

They are under different trade names AE25-15, AE 25-9; AEO 40, AEO 9 Adekatol SO 160, alcohols, C12-15, ethoxylates, Ales (crosslinking agents), C12-15, ethoxylates, Alfonic 1012-1040 Anapoe C13E8, BRE 15, Bio-Soft ES 600, C 1215AE30, C12-15 Pareth 3, C12-15 Pareth-12, C12-15 Pareth-9, Dobanol 25-7, Dobanol 25-9, Dobanox 251, Emersist 7232, Empilan KCL9 , Enordet AE 1215-1230, Enordet AE 1215 to 9.4, C12-15 ales ethoxylates, C 12-15 ethoxylated alcohols, Genapol 26L45, Genapol A 050, Genapol OX, Genapol OX 030, Genapol OX 060, Genapol OX 070 Genapol OX 100, Genapol OX 130, Imbentin C125 / 85, Imbentin L 125/094, Lialet 125/5, Lialet 125/7, Marlipal 025/50, Marlipal 025/70, Mulsifan RT 203/80, Musifan RT203 / 80 , Neodol 23-SE, Neodol 25-12, Neodol 25-3, Neodol 25-7, Neodol 25-7E, Neodol 25-9, Neonol P 1215-122, Neonol P1215-3, Neonol P 1215-6, Neonol P1215 -8, Neonol P 1215-9, Nonidet R12, Nonidet R7, Pareth 25, Pareth 25-12, Pareth 25-7, Pingpingjia 9, Rhodasurf 25-3, Rokanol DB 3, Sandoxylat A 25-7, Serdox NES, Serdox NES 3, Serdox NES 8, Slovasol 2530, Slovasol 257, Slovasol 3520R, Solvasol 2510, Soprophor K 202, T-DET 25-3S, Tergitol 25L, Tergitol 25L3, 25L5, Te rgitol, Tergitol 25L7, 25L9 Tergitol, Teric 12A, Teric 12A23, Teric 12A23B, Teric 12A3, 12A8 Teric, Teric T 12A, Teric T 12A6, 12A8 Teric T, Teric A 8, Tomadol 25 - 12, Tomadol 25 -3, Tomadol 25-7, Tomadol 25-9, among others.

For the case of BIO-SOFT N25 SERIES:

CH ₃ (CH ₂ ) _n - 0- (CH ₂ CH ₂ -O-) _y -H

n = 11 to 14

y = 1 to 5.

Family CAS No. 9016-45-9 belongs to the ethoxylated alkyl phenols of formula: R1-C6H4-0- (CH2-CH2-0) n -H

Where:

R1 = octyl, nonyl, dodecyl

n = 4 to 40

For detergents, octyl and nonyl are preferred, with n = 8 and n = 12,

For n less than 5 they are used as antifoam and liposoluble surfactant,

For n = 6 and 8 are very good surfactants,

For n greater than 10 as humectant, detergents, and liposoluble dispersants, For n greater than 20, they behave as very good detergents.

In particular, it is preferred to

nonil.

The structure of nonylphenolethoxylates is:

(CH 3) ₂ CH-CH ₂ -CH (CH 3) -CH ₂ -CH (CH 3) -C ₆ H ₄ -O- (CH ₂ CH ₂ -O) nH. Ethoxylated alkylphenols are under various trade names: Glycols, polyethylene, mono (nonylphenyl) ether (8CI); Arkopal 130; Arkopal 160 (Nonylphenoxy) polyethylene oxide; At 730; Ace Clean AD; Adekatol NP 1,100; Adekatol NP 660; Adekatol NP 675; Adekatol NP 686; Adekatol NP 690; Adekatol NP 710; AdekatolNP 760; Adekatol NP 900; Agrai; Agrai 600; Agrai LN; Agrai Plus; Akyporox NP105; Akyporox NP 95; Alfenol; Alfenol 18; Alfenol 28; Alfenol 8; Alkasurf NP; Alkasurf NP 11; AlphoX 200; AntaroxCO; Antarox CO 530; Antarox CO 730; Antarox CO 880; Arkopal 80; Arkopal 9; Arkopal No. 040; Arkopal No. 080; Arkopal No. 100; Arkopal No. 150; Arkopal No. 300; Arkopal No. 308; Atmer 508; B 315 (polyoxyalkylene); BLM; Berol 02; Berol 227; Berol 26; Berol 268; Berol 296; Biefenol No. 45; Blaunon No. 510; Jelly CCC; CO 630; CO 730; Canasol NF 1000; Carsonon No. 30; Carsonon No. 8; SINOPOL 908; among others.

The total amount of surfactant in the composition ranges from (1 to 95)% (w / w).

[0061] 3- Polar aprotic organic solvents are selected from the lactam family, with at least a hydrosolubility greater than 10 g / l at 1013 mbar, capable of completely dissolving the active principle. As are N-methylpyrrolidone, N-ethylpyrrolidone, etc.

May be non-lactam solvents with a dielectric constant greater than 30, such as dimethyl sulfoxide, propylene carbonate, acetonitrile and / or lactam solvents with preferably 3 to 6 C atoms and their N-methyl N-ethyl derivatives, which comply with the dielectric constant greater than 20, where some of its components are N-methylpyrrolidone, N-ethylpyrrolidone, etc.

It is preferable to use the solvent with CAS No. 872-50-4 (N-methylpyrrolidone), under different known trade names, as it is completely miscible in water, has relatively low toxicity, biodegradable by its polarity with €. = 32 and its intrinsic physical properties, which make it an excellent drug solubilizing agent, a good vehicle in veterinary, pharmacy and agro, for low polar drugs that have difficulty solubilizing.

Its concentration in the composition ranges from (5 to 75)% w / w. 4 - The cosolvent is not miscible in water, which may or may not be present; it is selected from the group of fatty acid methyl esters of different types of vegetable oil, which may be sunflower oil, being better than soybean, and even better palm oil and rapeseed. Also, in particular, the ester with CAS No. 12-62-9 (methyl oleate). A suitable relationship to be present in the formulation (when necessary) is with the present concentration of total surfactant, R = C / T, being 0.3 <R <0.8; where C = the cosolvent concentration and T = the total surfactant concentration.

Its concentration ranges from 0 to 30% w / w.

Defoamers, which may or may not be present and when present, are known to a skilled formulator, such as siliconated defoamers, polysiloxanes such as polydimethylsiloxanes. Of those present, they are in a concentration of 0 to 2% w / w.

6 - In the category of formulation stabilizers which may or may not be present are antioxidants (Vitamin E, BHT, etc.), UV absorbers such as cinnamic esters, 3,3-diphenyl 2-acrylates. cyano, hydroxy and / or alkoxy substituted benzophenones, N- (hydroxyphenyl) benzotriazools, etc. Suitable preservatives such as formaldehyde, p-hydroxybenzoic acid alkyl esters, sodium benzoate, thiazolinones, 2-dichlorobenzyl alcohol, etc.

Also, they may eventually contain thickeners, colorants, etc.

The stabilizers, which may be present, are in a concentration of 0 to 1% w / w.

General Preparation Procedure

In a suitable stirring vessel equipped with a heating device (heating jacket, coil, etc.) the established quantities of the non-water miscible co-solvent, the surfactant mixture, the formulation stabilizers, the defoaming agent are added together. , the preservatives and 90% of the aprotic dipolar organic solvent, being mixed by heating the mixture to a temperature between (45-55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of the organic solvent is added and a prudential time is stirred that it can be between a minimum of 1 h and a maximum of 2 hours, allowing to cool to room temperature, thus obtaining the final finished product.

Examples

[0072] The compositions of Emamectin Benzoate and

Abamectin:

Example 1:

Emamectin Benzoate (N ^Q CAS 137512-74-4) 20% w / v

CAS No 68131 -39-5 / CAS No 9016-45-9 Mixture of surfactants 27% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.35% w / v

Formaldehyde 40 0.5% w / v

Methyl Oleate (CAS No 1 12-62-9) 17% w / v

N-Methyl-2-pyrrolidone (CAS No 872-50-4) qsp 100% w / v. qsp = csp: enough for 100%. It is a way of placing as a main solvent because the density may vary slightly according to the moment conditions, so contemplate such variation and close the formulation to 100%.

[0073] The mixture of nonionic surfactants consists of 20% of oxyethylenated fatty alcohols of formula: R1 - O - (CH ₂ -CH ₂ -O) n H where R1 is a C13 linearalquil chain, and n is 9 ; and 80% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -0 - (CH ₂ -CH ₂ -O) n H where R 1 is nonyl and n is 35.

Procurement Procedure

The appropriate stirring vessel fitted with a heating device (heating jacket, coil, etc.) is added to the established amounts of methyl oleate, surfactant mixture, BHT, Defoamer, Formol 40 and 90% N-methylpyrrolidone. , and mixed by heating the mixture to a temperature between (45-55 ° C). The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of the N-methylpyrrolidone is added and a prudential time is stirred between a minimum of 1 hour and a maximum of 2 hours, allowing to cool to room temperature, thus obtaining the final finished product (Final Composition).

Example 2

Abamectin (CAS No 71 751 -41 -2) 10.8% w / v CAS No. Mixture of Surfactants 68131 -39-5 / N ⁹ CAS 9016-45-9— -18% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.35% w / v

Formaldehyde 40 0.5% w / v

Methyl Oleate (CAS No. 1 12-62-9) 7% w / v

N-Methyl-2-pyrrolidone (CAS No 872-50-4) qsp100% w / v

[0075] The mixture of nonionic surfactants consists of 70% oxyethylenated fatty alcohols of formula: R 1 -O- (CH ₂ -CH ₂ -O) n H where R1 is a C12 linearalquil chain, n is 5 ; and 30% ethoxylated alkyl phenols of formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) n-H, where R 1 is octyl and n is 20.

Procurement Procedure

In a suitable stirring vessel with heating device (heating jacket, coil, etc.) the established amounts of methyl oleate, surfactant mixture, BHT, defoamer, formaldehyde 40 and 90% N-methylpyrrolidone are added. The mixture is made by heating the mixture at a temperature between (45-55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of the N-methylpyrrolidone is added and stirred for a prudential time, which can range from a minimum of 1 hour to a maximum of 2 hours allowing to cool to room temperature, thus obtaining the final finished product (Final composition). .

Example3

Emamectin Benzoate (CAS No 137512-74-4) 42% w / v ( ^* )

CAS No 68131 -39-5 / CAS No 9016-45-9 Mix of Surfactants 40% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.35% w / v

Formaldehyde 40 0.5% w / v

N-Methyl-2-pyrrolidone (CAS No. 872-50-4) qsp 100% w / v

Note: ( ^* ) is 40% w / w.

[0077] The mixture of nonionic surfactants consists of 10% oxyethylenated fatty alcohols of formula: R 1 -O - (CH ₂ -CH ₂ -O) n H where R1 is a C15 linearalquil chain, n is 8 ; and 90% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -O- (CH ₂ -CH ₂ -O) _n - H where R 1 is dodecyl and n is 40. Procurement Procedure

In a suitable stirring vessel with heating device (heating jacket, coil, etc.) the established amounts of surfactant mixture, BHT, Defoamer, Formol 40 and 90% of N-methylpyrrolidone are added. mixture by heating the mixture to a temperature between (45-55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of N-methylpyrrolidone is added and a prudential time is stirred between a minimum of 1 hour and a maximum of 2 hours, allowing to cool to room temperature, thus obtaining the final finished product (Final Composition).

Example4

Abamectin (CAS No 71751 -41 -2) 18% w / v

CAS No. Mixture of Surfactants 68131 -39-5 / N ^Q CAS 9016-45-9 33% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.23% w / v

Formalin 40 0.9% w / v

Rapeseed oil fatty acid methyl esters 13% w / v

N-Methyl-2-pyrrolidone (CAS No 872-50-4) qsp100% w / v

[0079] The mixture of nonionic surfactants consists of 35% of oxyethylenated fatty alcohols of formula: R 1 -O- (CH ₂ -CH ₂ -O) _n - H wherein R1 is a C14 linear alkyl chain, and n is 7; and 65% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) n - H where R 1 is dodecyl and n is 30.

Procurement Procedure

In a suitable stirring vessel fitted with a heating device (heating jacket, coil, etc.), the established quantities of rapeseed oil fatty acid methyl esters, surfactant mixture, BHT, defoamer, formaldehyde 40 and 90% N-methylpyrrolidone, the mixture being made by heating the mixture to a temperature between (45 - 55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, add the rest of N-methylpyrrolidone and stir a prudential time, which can range from a minimum of 1 hour to a maximum of 2 hours, allowing to cool to room temperature, thus obtaining the final finished product (final composition).

Example 5:

Emamectin Benzoate (CAS No 137512-74-4) 15% w / v

Mixture of CAS-No. 68131 -39-5 / CAS-No. 9016-45-9— - 20% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.15% w / v

Formaldehyde 40 0.5% w / v

Sunflower oil fatty acid methyl esters 8% w / v

N-ethyl-2-pyrrolidone qsp 100% w / v

[0081] The mixture of nonionic surfactants consists of 50% oxyethylenated fatty alcohols of formula: R 1 -O- (CH ₂ -CH ₂ -O) n H where R1 is a C13 linearalquil chain, and n is 9 ; and 50% of ethoxylated alkyl phenols of formula: where R 1 is nonyl and is 30, R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) n -H.

Procurement Procedure

The appropriate stirring vessel fitted with a heating device (heating jacket, coil, etc.) shall be added to the established quantities of sunflower oil methyl esters, surfactant mixture, BHT, defoamer, formaldehyde 40 and 90% of N-ethylpyrrolidone, the mixture being made by heating the mixture to a temperature between (45 - 55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of the N-ethylpyrrolidone is added and a prudential time that can range from a minimum of 1 hour to a maximum of 2 hours is stirred, allowing to cool to room temperature, thus obtaining the final finished product (final composition).

Example 6:

Abamectin (CAS No 71751 -41 -2) 4% w / v

CAS No 68131 -39-5 / CAS No 9016-45-9 Mixture of surfactants 27% w / v

BHT (Butyl hydroxy toluene) 0.2% w / v

Silicon Defoamer 0.35% w / v

Formaldehyde 40 0.5% w / v

Methyl Oleate (CAS No 1 12-62-9) 17% w / v

N-methyl-2-pyrrolidone (CAS No. 872-50-4) qsp 100% w / v [0083] The mixture of nonionic surfactants consists of 90% oxyethylenated fatty alcohols of formula: R 1 -O- (CH ₂ -CH ₂ -O) _n - H wherein R1 is a C12 chain linearalquil n is 3; and 10% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -O- (CH ₂ -CH ₂ -O) _n - H where R 1 is octyl and n is 10,

Procurement Procedure

In a suitable stirring vessel with heating device (heating jacket, coil, etc.) the established quantities of methyl oleate, surfactant mixture, BHT, defoamer, formal 40 and 90% N-methylpyrrolidone are added. The mixture is made by heating the mixture to a temperature between (45 - 55) ° C. The entire amount of the active ingredient is added with stirring and stirred until complete final dissolution to give a homogeneous mixture. Finally, the rest of the N-methylpyrrolidone is added and stirred for a prudential time, which can range from a minimum of 1 hour to a maximum of 2 hours, allowing to cool to room temperature, thus obtaining the final finished product (final composition). ).

Essay

Various dilutions were made in 0.5% w / w water in all cases, and particle sizes were analyzed at the beginning and end of the established 12 h time period, up to 24 h employing a Malven NanosizerAS analyzer equipment with detector 175 and DTS (V 4.00) software, scattered light technique (DLS), where particle motion velocity distribution is analyzed by measuring dynamic fluctuations in light scattering intensity caused by Brownian motion of the particle. This technique gives a radius of hydrodynamic diameter which is calculated by the Stokes-Einstein equation.

The 0.5% dilution represents a high active ingredient final concentration value which comprises any actual dose level dilution per hectare.

In the above five (5) compositions, when diluted in water by 0.5% (0.5 parts of the composition in 99.5 parts of water), slightly bluish clear aqueous compositions are formed, some translucent to slightly opaque, in which the active ingredient, the particles formed in the aqueous microemulsion all have a diameter size of less than 150 nm, remaining stable for a minimum of 12 h, sometimes reaching 24 h and 36 h.

Note: Compositions diluted in 0.5% water.

A composition is stable over time if the particle size does not exceed 500 nm and no precipitation or crystallized material is observed. With compositions 1, 3 and 5, dilutions in 0.1% water (1 part of the composition in 99.9 parts of water) have now been made, forming slightly bluish clear aqueous compositions, some translucent to very slightly opaque, in which the active ingredient, the particles formed in the aqueous microemulsion are all less than 150 nm in diameter in size, remaining stable for a minimum of 12 h and in some cases up to 24 h.

Composition,

D97 nm start D97 nm 12h D97 nm 24h example

1 34.5 64.7 1 12.5

3 38.8 77.7 104.4 5 70.7 <101.8

Note: Compositions diluted in 0.1% water.

A composition is stable over time if the particle size does not exceed 500 nm and no precipitation or crystallized material is observed. To compare them, two (2) conventional non-aqueous compositions A and B containing 10% Emamectin Benzoate were prepared. Composition A was a WP-type formulation finely divided into a milled powder of less than 45 µm containing 2.5% dispersing agent (sodium lignosulfonate), 3.4% suspending wetting agent (10M ethoxylated nonylphenol in silica). ), 1% Aerosil 200 and the rest of the composition was 325 mesh kaolin.

Composition B was an EC-type formulation containing 6.5% of a mixture of nonionic emulsifying agents, and 30% of N-methylpyrrolidone and the remainder of the Xylene solvent.

The two (2) compositions, A and B, were diluted in 0.5% water (0.5 parts of the composition in 99.5 parts of water).

Composition A, when diluted with water, formed a suspension in which the average dispersed particle size was approximately 7.5 μιη. After 12 h, large amounts of particulate material were observed, with some 3 mm sediment size.

Composition B, when diluted with water, formed an acceptable milky-type emulsion whose mean particle size was 1.5 μιη, where at the end of 12h the average size increased to greater than 6 µm. μιη and at the end of 24 h a large amount of sedimented particulate material was observed, the size of which was 2 mm.

Physicochemical tests

Low temperature storage stability

100 mL of formulation is maintained at 0 ° C for seven days and the amount of oily or solid material that can separate. Centrifugation is done and phase separation is observed.

1 hour 7 days Result

Solid Volume 0 0 Stable at 0 ° C separated (mL)

Oil volume 0 0 Stable at 0 ° C separately

The tests performed after the greenhouse test at 54 ° C for 14 (fourteen) days were:

Foam Persistence

Measurement of the volume of foam formed on 1 mL of sample with sufficient water to complete 100 mL after shaking by inversion.

Time Foam Volume Formed

30 "4 mL

r 4 mL

3 '3.5 mL

12 '3 mL Product viscosity at 20 ° C 323 cPoise

Microemulsion stability

In 1 mL of sample and 99 mL of test water the beaker is inverted 10 times, leaving at a temperature of 30 ° C, observing whether the precipitate or supernatant separates.

Time Precipit Volume Volume

separate supernatant

separate

30'0 mL 0 mL

2 hours 0 mL 0 mL

24 hours 0 mL 0 mL Note: No changes or shifts in specifications were observed in the stability of the microemulsion formed by dilution in water immediately after the product has passed the heat stability test.

Field trials against caterpillars

A dose of 75 cc / ha was applied and the number of caterpillars killed over the days was evaluated.

Results

It was observed that in equal concentration of active in the formulations and equal dose / ha there are clear differences as to the type of formulation, observing that the MEC formulation presents in the same days larger number of dead caterpillars, determining an improvement in the bioefficacy of the MEC formulation.

Field trials against bed bugs Evaluation of control and survival time of bed bugs in the experimental field:

Number of Bed Bugs: 43

A dose of 75 ml / ha of an Emamectin Benzoate MEC formulation of the present invention was applied in the experimental field. The number of bed bugs killed at 2 hours, 16 hours, 20 hours, 30 hours and 18 hours after application of the formulation was counted.

Results:

[0097] The formulation is effective for controlling bed bugs in crops. Its maximum effectiveness is obtained 48 hours after application.

Claims

1 - NON-Aqueous Liquid Pesticide Composition, characterized in that it comprises at least one sparingly soluble or water-insoluble organic pesticide in a concentration of 4.0 to 40% w / w; a balanced mixture of nonionic surfactants at a concentration of 1 to 95% w / w; a polar aprotic organic solvent or more than one at a concentration of 5 to 75% w / w, a non-water miscible cosolvent at a concentration of 0 to 30% w / w, a defoamer at a concentration of 0 to 2% w / w / eg a stabilizer at a concentration of 0 to 1% w / w.

NON-Aqueous LIQUID PROGUICIDE COMPOSITION according to claim 1, characterized in that once diluted in water for its application forms a microemulsion, yielding nanoparticles with particle size from 10 to 500 nm.

NON-Aqueous Liquid Pesticide Composition according to Claim 2, characterized in that once diluted in water for its application, it forms a microemulsion, resulting in nanoparticles smaller than 200 nm.

A non-aqueous liquid liquid composition according to claim 3, characterized in that once diluted in water for its application forms a microemulsion, resulting in nanoparticles smaller than 100 nm.

NON-Aqueous Liquid Pesticide Composition according to Claim 4, characterized in that once diluted in water for its application forms a microemulsion and yields nanoparticles less than 40 nm in size.

A non-aqueous liquid pesticide composition according to Claim 1, characterized in that the pesticide is selected from the group belonging to the chemical family of Avermectins.

Aqueous non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is selected from the group consisting of abamectin and emamectin benzoate. A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 4.0 to 40% w / w.

A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 40% w / w.

A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 20% w / w.

A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 18% w / w.

A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 15% w / w.

A non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 10.8% w / w.

Aqueous non-aqueous liquid pesticide composition according to claim 6, characterized in that the pesticide is in a concentration of 4% w / w.

PRAGUICIDE COMPOSITION according to claim 1, characterized in that the balanced mixture of nonionic surfactants is formed by 10 to 90% of oxyethylene fatty alcohols of the formula: R1 -O- (CH ₂ -CH ₂ - 0) n-H wherein R1 is a C12 to C15 straight chain alkyl and n is from 0 to 9; and 10 to 90% of ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -0- (CH2-CH2-0) _n - H where R 1 is octyl, nonyl or dodecyl en is between 4 to 40.

A non-aqueous liquid pesticide composition according to claim 15, wherein R 1 of the formula: R 1 - O- (CH ₂ -CH ₂ -0) nH is a C 13 to C 14 linear alkyl chain, from 2 to 9 Aqueous non-aqueous liquid composition according to claim 15, characterized in that R 1 of the formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) _n -H, is nonyl or dodecyl and is comprised between 10 to 35.

A non-aqueous liquid pesticide composition according to claim 15, characterized in that the balanced mixture of nonionic surfactants is formed by 20% of oxyethylene fatty alcohols of formula: Ri- O- (CH ₂ -CH ₂ -O) n- H and 80% ethoxylated alkyl phenols of formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) _n -H.

A non-aqueous liquid pesticide composition according to claim 15, characterized in that the balanced mixture of nonionic surfactants is formed by 35% of oxyethylene fatty alcohols of the formula: R1 - O- (CH ₂ -CH ₂ -O) _n - H and 65% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O)

Aqueous liquid non-aqueous composition according to Claim 15, characterized in that the balanced mixture of nonionic surfactants is formed by 50% of oxyethylene fatty alcohols of the formula: R1 - O - (CH ₂ -CH ₂ -O) n - H and 50% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ - 0- (CH ₂ -CH ₂ -O) _n - H.

Aqueous liquid non-aqueous composition according to Claim 15, characterized in that the balanced mixture of nonionic surfactants is formed by 70% of oxyethylene fatty alcohols of the formula: R1 - O- (CH ₂ -CH ₂ -0) _n - H and 30% ethoxylated alkyl phenols of formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -0) _n -H.

A non-aqueous liquid pesticide composition according to claim 15, characterized in that the balanced mixture of nonionic surfactants is formed by 90% oxyethylene fatty alcohols of the formula: R1 - O- (CH ₂ -CH ₂ -0) n- H and 10% ethoxylated alkyl phenols of formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -0) _n -H.

A non-aqueous liquid pesticide composition according to claim 1, characterized in that the polar aprotic organic solvents are selected from the lactam family group, preferably having 3 to 6 C atoms and N-methyl N-ethyl derivatives thereof. .

A non-aqueous liquid pesticide composition according to claim 23, characterized in that the aprotic organic solvents from the group consisting of N-methylpyrrolidone and N-ethylpyrrolidone.

A non-aqueous liquid pesticide composition according to claim 24, characterized in that the polar aprotic organic solvents are in a concentration of 25% to 50%.

A non-aqueous liquid pesticide composition according to claim 1, characterized in that the non-water miscible cosolvent is selected from the group of fatty acid methyl esters of a different type of vegetable oil.

A non-aqueous liquid pesticide composition according to claim 26, wherein the non-water miscible cosolvent is selected from the group of fatty acid methyl esters of sunflower, soybean, palm and rapeseed vegetable oils.

A non-aqueous liquid pesticide composition according to claim 26, characterized in that the non-water miscible cosolvent is methyl oleate.

A non-aqueous liquid pesticide composition according to claim 28, characterized in that the methyl oleate is in a concentration of 10 to 20%.

A non-aqueous liquid pesticide composition according to claim 26, characterized in that the non-water miscible cosolvent is composed of fatty acid methyl esters of sunflower vegetable oils.

A non-aqueous liquid pesticide composition according to claim 30, characterized in that the fatty acid methyl esters of sunflower vegetable oils are in a concentration of 10 to 15%.

A non-aqueous liquid pesticide composition according to claim 1, characterized in that the defoamer is selected from the group of emulsion-shaped silicon defoamers.

A non-aqueous liquid pesticide composition according to claim 32, characterized in that the defoamer is a polydimethylsiloxane.

A non-aqueous liquid pesticide composition according to claim 33, characterized in that the defoamer is polydimethylsilicone. 35. Aqueous non-aqueous liquid pesticide composition according to claim 34, characterized in that the polydimethylsilicone is in a concentration of 0.1 to 0.5%.

A non-aqueous liquid pesticide composition according to claim 1, characterized in that the stabilizers are selected from the group of antioxidants, UV absorbers, preservatives and thickeners.

37. Aqueous non-aqueous liquid pesticide composition according to claim 36, characterized in that the antioxidants are selected from the group consisting of Vitamin E and Butyl hydroxytoluene.

A non-aqueous liquid pesticide composition according to claim 37, characterized in that Butyl hydroxytoluene is in a concentration of 0.2 to 0.5%.

A non-aqueous liquid pesticide composition according to claim 36, characterized in that the UV absorbers are selected from the group of cinnamic esters, 3,3-diphenyl-2-cyano acrylates, hydroxy-substituted benzophenones and / or alkoxy, and the N- (hydroxyphenyl) benzotriazoles.

A non-aqueous liquid pesticide composition according to claim 36, characterized in that the preservatives are selected from the group of formaldehyde, p-hydroxybenzoic acid alkyl esters, sodium benzoate, thiazolinones and 2-dichlorobenzyl alcohol.

NON-Aqueous LIQUID PROGUICIDE COMPOSITION according to Claim 40, characterized in that the alkyl esters of p-hydroxybenzoic acid sodium benzoate are in a concentration of 0.1 to 0.5%.

A non-aqueous liquid pesticide composition according to claim 1, characterized in that it optionally has other thickeners, colorants and other adjuvants of the formulation.

A non-aqueous liquid pesticide composition according to claim 42, characterized in that the thickeners, colorants and other adjuvants of the formulation are in a concentration of 0.1 to 0.5%. A non-aqueous liquid pesticide composition according to any one of claims 1 to 43, characterized in that it is used for the control of insects, mites and nematodes in crops.

PREPARATION PROCEDURE for preparing the pesticide composition of claims 1 to 44, comprising the following steps:

(a) Aggregate in a stirring vessel equipped with a heating device the established quantities of the non-water miscible cosolvent, the surfactant mixture, the formulation stabilizers, the defoaming agent, the preservatives and the 90% aprotic dipolar organic solvent;

b) mixing the components (a) heating the mixture to a temperature between 45-55 C ^Q;

c) Aggregate with agitation all the established quantity of the active principle;

(d) Stir until completely dissolved and a homogeneous mixture is formed;

e) Aggregate the remaining 10% of the polar aprotic organic solvent;

f) Stir until homogeneous mixture is formed;

g) Allow the mixture to cool to room temperature.

Preparation according to claim 45, characterized in that the active ingredient is selected from the group of pesticides belonging to the Avermectin family.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is selected from the group consisting of abamectin and emamectin benzoate.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 4.0 to 40% w / w.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 40% w / w. PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 20% w / w. PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 18% w / w.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 15% w / w.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 10.8% w / w.

PREPARATION PROCEDURE according to Claim 45, characterized in that the pesticide is in a concentration of 4% w / w.

Preparation method according to Claim 45, characterized in that the balanced mixture of nonionic surfactants is formed by 10 to 90% of oxyethylene fatty alcohols of the formula: R 2 O - (CH ₂ -CH ₂ -O) - H, where R 1 is a C 12 to C 15 alkyl straight chain, and n is 0 to 9; and10 to 90% of ethoxylated alkyl phenols of the formula: R, -C ₆ H ₄ -0- (CH ₂ - CH ₂ -O) _n - H where R 1 is octyl, nonyl or dodecyl en is between 4 to 40.

Preparation according to Claim 55, characterized in that the balanced mixture of nonionic surfactants is formed by 20% oxyethylene fatty alcohols of the formula: R 1 - O - (CH ₂ -CH ₂ -O) _n - H and 80% ethoxylated alkyl phenols of formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) _n -H.

57- Preparation Procedure, according to claim 55, wherein the balanced blend of nonionic surfactants is formed by 80% of oxyethylenated fatty alcohols of formula: R1 - O (CH ₂ -CH ₂ -) _n - H and 10 to 20% ethoxylated alkyl phenols of the formula: R 1 -C ₆ H ₄ -0- (CH ₂ -CH ₂ -O) _n -H.

Preparation according to Claim 45, characterized in that the polar aprotic organic solvents are selected from the group of the lactam family, preferably having 3 to 6 C atoms and their N-methyl and N-ethyl derivatives.

Preparation according to Claim 45, characterized in that the polar aprotic organic solvents are selected from the group consisting of N-methypyrrolidone and N-ethylpyrrolidone. Preparation process according to claim 59, characterized in that the polar aprotic organic solvents are in a concentration of 5 to 75% w / w.

Preparation according to Claim 45, characterized in that the non-water miscible cosolvent is selected from the group of fatty acid methyl esters of a different type of vegetable oil.

Preparation according to Claim 45, characterized in that the non-water miscible cosolvent is selected from the group of fatty acid methyl esters of sunflower, soybean, palm and rapeseed vegetable oils.

Preparation according to claim 62, characterized in that the non-water miscible cosolvent is in a concentration of 0 to 30%.

Preparation according to Claim 45, characterized in that the defoamer is selected from the group of emulsion-shaped silicone defoamers.

PREPARATION PROCEDURE according to Claim 64, characterized in that the defoamer is in a concentration of 0 to 2%.

Preparation according to Claim 45, characterized in that the stabilizers are selected from the group of antioxidants, UV absorbers, preservatives and thickeners.

PREPARATION PROCEDURE according to Claim 66, characterized in that the stabilizers are in a concentration of 0 to 1%.

Preparation method according to claim 45, characterized in that it optionally contains other thickeners, colorants and other adjuvants of the formulation.

A method for eliminating insects, mites and neemodes in crops, applied according to the formulation according to any one of claims 1 to 44, characterized in that it is applied to insects, mites or nematodes and / or their habitat.