EC formulations comprising organophosphate insecticides

Abstract

Solvent formulations under EC form comprising (% by weight): 10-40% of one or more compounds having an insecticidal activity selected from the organophosphate class; 1-20% of an additive (A) methyl or ethyl esters of carboxylic acids having a C.sub.10-C.sub.20 chain, saturated or unsaturated, or mixtures thereof, the fatty acids deriving from vegetal oils; 0.5-10% of an additive B) of a cellulose derivative soluble in the organic solvent of EC formulation; 3-15% of one or more surfactants selected from non ionic and anionic surfactants, or thereof mixtures; the complement to 100% being of one or more organic solvents having the following characteristics: capable to solubilize the active principle, expressed as % by weight, at room temperature (20-25 C.) for at least 5%; preferably 10%, more preferably at least 20%, immiscible with water.

Claims

1. An emulsifiable concentrate (EC formulation) comprising (% by weight): 10-40% of one or more actives selected among organophosphate compounds having the following structure (formula (I)): ##STR00003## wherein: L.sub.1 is oxygen or sulphur, L.sub.2 and L.sub.3, same or different from each other, are selected from oxygen, sulphur and a NH group, with the proviso that at least one of L.sub.1, L.sub.2, and L.sub.3 is sulphur and at least one of L.sub.1, L.sub.2, and L.sub.3 is oxygen, M is selected from oxygen, sulphur and NH; 1-20% of methyl or ethyl esters of fatty acids having a C.sub.10-C.sub.20 chain, saturated or unsaturated, and mixtures thereof (additive (A)); 0.5-10% of a cellulose derivative soluble in the organic solvent of the EC formulation selected from cellulose alkylethers and carboxy alkyl cellulose esters (additive (B)); 3-15% of one or more surfactants selected from non ionic and anionic surfactants, and mixtures thereof; the complement to 100% being one or more organic solvents having the following characteristics: capable of solubilizing the one or more active, expressed as % by weight, at room temperature (20-25 C.) for at least 5%; and immiscible with water; wherein the organic solvents are selected from the following group: alkylbenzenes having a number of carbon atoms from 7 to 20 and mixtures thereof, the alkyl being linear or branched; and linear or branched C.sub.7-C.sub.9 alkyl esters of acetic acid.

2. The formulation according to claim 1, wherein the organophosphate compounds have the following formula (II): ##STR00004## wherein: L.sub.1, L.sub.2, L.sub.3 and M are as defined above; A is selected from the group consisting of: (1) a linear or branched alkyl C.sub.1-C.sub.10 alkyl, optionally containing one or more heteroatoms, preferably one or two, selected from O, S, CO, and SO; wherein the hydrogen atoms of the C.sub.1-C.sub.10 alkyl chain are optionally substituted with one or more of the following groups: halogen; CH(COOR.sub.3), and a radical of an ester of succinic acid of formula CH(COOR.sub.3)CH.sub.2(COOR.sub.3), R.sub.3 being C.sub.1-C.sub.4 alkyl; wherein when the C.sub.1-C.sub.10 alkyl is linear, the chain end carbon atom is optionally substituted with one or more halogen atoms; when the C.sub.1-C.sub.10 alkyl is C.sub.1, it is monosubstituted or disubstituted; when the C.sub.1-C.sub.10 alkyl is monosubstituted C.sub.1, one hydrogen atom of the alkyl is substituted with one of the following groups: (CO)NH(CH.sub.3), 1,3,4-thiadiazol-2(3H)-one-yl, wherein the hydrogen atom of the carbon atom at position 5 of the ring is substituted with a group R.sub.3O alkoxy group wherein R.sub.3 is as defined above; phthalimido; 3,4-dihydro-4-oxobenzo[d]-[1,2,3]-triazinyl, 2,3-di-hydro-2-oxo-1,3-benzoxazolyl wherein the hydrogen atom of the carbon atom at position 6 of the ring is substituted with one halogen atom; and 2-oxo[1,3]-oxazol[4,5-b]pyridin-(2H)-yl wherein the hydrogen atom of the carbon atom at position 6 of the pyridinyl ring is substituted with halogen; and when the C.sub.1-C.sub.10 alkyl is disubstituted C.sub.1, the substituents are respectively an ethoxycarbonyl group and a phenyl group; (2) an aromatic ring of 6 carbon atoms having one or two substituents selected from the following group: halogen; CN; NO.sub.2; SCH.sub.3; R.sub.3 and COOR.sub.3, wherein R.sub.3 is as defined above; and (3) a substituent selected from the following: pyridinyl substituted with one or more halogen atoms; (CO)CH.sub.3, 2-oxo-2H-chromenyl wherein two hydrogen atoms, each linked to a different carbon atom of the ring, are substituted respectively with a halogen group and a R.sub.3 group as defined above; pyrimidinyl wherein a hydrogen atom of one or two carbon atoms of the ring is substituted with a group selected from halogen, R.sub.3 as defined above, and diethylamino; 1,2-oxazolyl wherein the hydrogen atom of a carbon atom of the ring is substituted with a phenyl group; pyrazolyl substituted with one phenyl group, said phenyl being optionally substituted with an halogen atom; 1,6-dihydro-6-oxo-pyridazinyl wherein a hydrogen atom of a carbon atom of the ring is substituted with a phenyl group; and R.sub.1 and R.sub.2, same or different from each other are: hydrogen, and linear or branched C.sub.1-C.sub.10 alkyl, wherein when the alkyl is linear, the one or two COORS groups are present on the chain end carbon atom, wherein R.sub.3 is as defined above.

3. The formulation according to claim 1 wherein the organophosphate compounds are selected from the group consisting of: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlofenthion, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, heptenophos, isofenphos-methyl, isopropyl-O-(methoxyamino thiophosphoryl) salicylate, isoxathion, malathion, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl, profenofos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, tebupirimfos, temephos, terbufos, thiometon, triazophos, trichlorfon, and vamidothion.

4. The formulation according to claim 3 wherein the organophosphate compounds are selected from the group consisting of chlorpyrifos, chlorpyrifos methyl, dimethoate and phosmet.

5. The formulation according to claim 1 wherein the methyl and/or ethyl esters of fatty acids having a C.sub.10-C.sub.20 chain, and mixtures thereof (additive (A)) are obtained by transesterification of vegetal oils selected from rape oil, soya oil, sunflower seed oil and canola oil with methyl or ethyl alcohol; the chain of said C.sub.10-C.sub.20 acids optionally contains one or more unsaturations of the ethylene type, in a number not higher than 3 and in alternated positions along the chain.

6. The formulation according to claim 5 wherein the methyl and/or ethyl esters of fatty acids having a C.sub.10-C.sub.20 chain, and mixtures thereof (additive (A)) are characterized by the following analytical parameters: TABLE-US-00004 Acid value (mg KOH/g) 1 Iodine value (g I.sub.2/100 g) 105-120 Residual water (% by weight) 0.2 Density at 25 C. (g/ml) 0.875-0.877.

7. The formulation according to claim 1 wherein the additive (B) is in an amount, expressed as percent by weight with respect to additive LA), of between 5 and 40%, the amount of additive (B), with respect to the composition of the solvent formulation under the EC formulation (% by weight) being in the range 0.5% and 8%.

8. The formulation according to claim 1 wherein the alkyl of the alkylethers of cellulose is C.sub.1-C.sub.5 and in the carboxyalkylcellulose esters the ester group has a C.sub.1-C.sub.4 alkyl chain and the alkyl of carboxyalkylcellulose is C.sub.1-C.sub.4.

9. The formulation according to claim 1 wherein the non ionic surfactants are selected from the group consisting of: linear or branched polyethoxylated C.sub.10-C.sub.18 fatty alcohols, wherein the ethoxyl number (EO) ranges from 5 to 10; polyethoxylated castor oil wherein the ethoxyl number ranges from 15 to 40; polyethoxylated distyrylphenols having an ethoxyl number between 12-25; polyethoxylated tristyrylphenols having an ethoxyl number between 15 and 40; C.sub.12-C.sub.18 mono- di and tri-esters of polyethoxylated sorbitan wherein the ethoxyl number ranges from 4 to 20; C.sub.10-C.sub.16 mixtures of alkyl polyglycosides optionally polyethoxylated or polypropoxylated wherein said alkylpolyglycosides have a different ethoxyl or propoxyl number, comprised between 10 and 25; polyethoxylated-polypropoxylated C.sub.8-C.sub.14 aliphatic alcohols; and polyaryl phenolethoxylate wherein the ethoxyl/propoxyl number is between 15 and 40.

10. The formulation according to claim 1 wherein the anionic surfactants are selected from the group consisting of: alkaline or alkaline-earth salts of C.sub.8-C.sub.16 alkylbenzensulphonates; and alkaline or earth-alkaline salts of C.sub.10-C.sub.14 alkylsulphates.

11. The formulation according to claim 1 wherein a mixture of non ionic and anionic surfactants is included in the formulation.

12. The formulation according to claim 11, wherein the percentage of non ionic surfactants is in the range from 40 to 80% with respect to the total percent weight of the surfactants of the EC formulation.

13. The formulation according to claim 1 comprising as optional components pesticides of classes different than organophosphates, said optional pesticides being soluble in the one or more organic solvent at the used concentrations, the solvent percentage being decreased by an amount equal to that of the optional pesticides added.

14. A process for preparing the formulation of claim 1 comprising the following steps: a) solubilization of the organophosphate compounds and optional pesticides in the one or more organic solvent used for the EC preparation, b) addition of one or more surfactants selected from non ionic and anionic surfactants and mixtures thereof, c) addition of the additive (A) and of additive (B), optionally by heating at temperatures not higher than 40 C.

15. A method of reducing odor associated with organophosphates present in a composition, the method comprising (a) providing a solution having one or more organophosphate compounds in an organic solvent, to which one or more surfactants selected from non-ionic and anionic surfactants or a mixture thereof is added, wherein the one or more organophosphates are defined by formula I of claim 1; (b) adding additives A) and B) according to claim 1, thereby obtaining an emulsifiable concentrate (EC); and (b) diluting the EC with water at an application dose prior to field distribution.

Description

EXAMPLES

(1) Characterization

(2) Acid Value

(3) The determination is carried out according to AOCS cd 3d-63.

(4) Iodine Value

(5) The determination is carried out according to Oleon OA-020.

(6) Residual Water

(7) The determination is carried out according to AOCS Ca 2e-84.

(8) Density

(9) The determination is carried out according to ISO 3675.

(10) Odour Evaluation

(11) A field application in an orchard has been simulated by using an atomizer. 300 ml of the formulated product have been diluted in 100 l (liters) of water. About 1500 l/ha have been used.

(12) A group of 9 persons was trained for odour evaluation according to the following score numerical scale:

(13) TABLE-US-00002 0 No odour 1 The operator perceives an unusual odour, but he cannot be sure if it can be attributed to the insecticidal treatment. 2 The operator perceives an unusual, but not unpleasant, odour, that he attributes to the insecticidal treatment 3 The operator perceives an unusual odour, slightly unpleasant, that he attributes to the insecticidal treatment 4 The operator perceives an unpleasant odour and he feels unconfortable to stay near the treated area 5 The operator perceives a very unpleasant odour and he feels as air is almost unbreathable to the point that he cannot stay in that place for a long time. 6 The odour perceived is extremely unpleasant to the extent that for him it is impossible to remain in that place.

(14) Three evaluation meeting assessments respectively at 2, 6 and 24 hours from the application in field have been overall carried out. The numerical values of the scores processed by statistical computing by using an ARM software. The statistical analysis has been based on Bartlett's test and Student-Newman-Keuls (S-N-K) multiple comparison test.

Example 1

(15) Preparation of an EC Formulation Containing Chlorpyriphos-Methyl

(16) 23 g of technical chlorpyriphos-methyl having 97% purity are mixed with 52.29 g of Solvesso 150 ND under stirring. 6.9 g of Geronol FF6E (mixture of calcium dodecylbenzenesulphonate and polyarylphenol ethoxylated wherein dodecylbenzene sulphonate <15% by weight and polyarylphenol ethoxylated is comprised between about 25% and about 65% by weight, the difference to 100 being solvents and 2.96 g of Geronol FF4E (mixture of calcium dodecylbenzenesulphonate and polyarylphenol ethoxylated wherein dodecylbenzene sulphonate is comprised between 25% and about 50% and polyarylphenolethyoxylated <25%, the difference to 100 being solvents, are added. Then about 14.85 of a mixture containing, as % by weight, 77% (11.43 g) of biodiesel and 23% (3.42 g) of ethylcellulose are added under stirring by heating at 40 C.

Example 2

(17) The preparation of Example 1 was repeated but omitting the addition of the additive of the invention and adding amounts of solvent equal to those of biodiesel (11.43 g) and ethylcellulose (3.42 g) of example 1.

Example 3

(18) Evaluation of the Odour of the Formulation of Example 1 and of Example 2 Comparative

(19) The method described in the characterization was used by employing the compositions of Example 1 and of example 2 comparative.

(20) The results obtained (score) were the following:

(21) TABLE-US-00003 Composition Example 1 0.9 Composition comparative 2.6

(22) The difference between the two score values was found statistically significant. This example shows that by using the formulation of Example 1 it is possible to reduce the odour of about 65% with respect to the formulation of Example 2 Comparative.