SOLID FORMULATION OF INSECTICIDAL MIXTURES

Abstract

The invention relates to solid formulations (especially water-dispersible granules) of tetramic acid derivatives and mixtures of these tetramic acid derivatives, to a process for production thereof and to the use thereof for application of the active ingredients present.

Claims

1. Solid composition in the form of water-dispersible granules comprising: a. tetramic acid derivative of formula (I) ##STR00023## in which W and Y are independently hydrogen, C1-C4-alkyl, chlorine, bromine, iodine or fluorine, X is C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine or iodine, A, B and the carbon atom to which A,B are bonded are C3-C6-cycloalkyl substituted by an optionally C1-C4-alkyl- or C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.2-alkyl-substituted alkylenedioxy group that forms a 5-membered or 6-membered ketal together with the carbon atom to which said group is bonded, G is hydrogen (a) or is one of the groups ##STR00024## in which E is a metal ion or an ammonium ion, M is oxygen or sulfur, R1 is straight-chain or branched C1-C6-alkyl, R2 is straight-chain or branched C1-C6-alkyl. b. at least one basic salt, c. at least one dispersant, d. at least one wetting agent, e. at least one filler, f. at least one structure former, g. optionally a complexing agent, h. optionally one or more further active ingredients, and i. optionally one or more further customary adjuvants and formulation auxiliaries.

2. Composition according to claim 1, wherein component a) in the composition comprises a compound of formula (I) ##STR00025## wherein TABLE-US-00012 W X Y A B CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Cl CH.sub.3 CH.sub.3 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Cl CH.sub.3 CH.sub.3 Br

3. Composition according to claim 1, wherein component a) is a compound of formula ##STR00032##

4. Composition according to claim 1, wherein component b) is selected from the group consisting of ammonium carbonate, ammonium hydrogencarbonate and diammonium hydrogenphosphate (DAHP).

5. Composition according to claim 1, wherein component b) is DAHP.

6. Composition according to claim 1, wherein component c) is a dispersant from the group consisting of sodium salts of the copolymers of maleic acid and olefins and sodium salts of copolymers of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, optionally sodium salts of copolymers of methacrylic acid and styrene and modified copolymers of methacrylic acid and styrene.

7. Composition according to claim 1, wherein component d) is selected from the group consisting of sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, optionally sodium salts of alkylated naphthalenesulfonates.

8. Composition according to claim 1, wherein component e) is selected from the group consisting of kaolin, rutile and silicon dioxide, and is optionally kaolin.

9. Composition according to claim 1, wherein component f) is selected from the group consisting of polymethylurea resins.

10. Composition according to claim 1, wherein component g) is selected from the group consisting of Na.sub.4EDTA.

11. Composition according to claim 1, wherein component h) is selected from the group consisting of imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, flubendiamid, tetraniliprole, cyclaniliprole; spirodiclofen, spiromesifen, spirotetramat, abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifuron, indoxacarb, metaflumizone, methoxyfenozid, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, sulfoxaflor, triflumuron, optionally ethiprole and flupyradifuron.

12. Composition according to claim 1, comprising a. compound of formula (I) ##STR00033## where: W is methyl, X is chlorine or methyl, Y is chlorine, bromine or methyl, A, B and the carbon atom to which A,B are bonded are saturated C6-cycloalkyl substituted by an alkylenedioxy group which, together with the carbon atom to which said group is bonded, forms a 5-membered or 6-membered ketal, G is hydrogen (a) or is one of the groups ##STR00034## in which M is oxygen, E is one metal ion equivalent or an ammonium ion, R.sup.1 is straight-chain or branched C.sub.1-C.sub.4-alkyl, R.sup.2 is straight-chain or branched C.sub.1-C.sub.4-alkyl, b. at least one dispersant of the polycarboxylate type, c. at least one anionic wetting agent, d. at least one inert filler, e. at least one structure former, f. at least one complexing agent, g. optionally one or more further active insecticidal ingredients, h. optionally one or more further adjuvants.

13. Composition according to claim 1, comprising a compound of formula (I) selected from the following compounds: TABLE-US-00013 (I) W X Y A B CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Cl CH.sub.3 CH.sub.3 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Cl CH.sub.3 CH.sub.3 Br b. at least one inorganic basic ammonium salt selected from the group consisting of ammonium carbonate, ammonium hydrogencarbonate and diammonium hydrogenphosphate (DAHP), c. at least one dispersant of the polycarboxylate type selected from the group of hydrophobically modified comb-like polymers comprising polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, a copolymer of maleic acid or maleic anhydride with an olefin, a copolymer of acrylic acid and itaconic acid, a copolymer of methacrylic acid and itaconic acid, a copolymer of maleic acid or maleic anhydride and styrene, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylate, a copolymer of acrylic acid and vinyl acetate, copolymers of methacrylic acid and styrene, modified copolymers of methacrylic acid and styrene, a copolymer of maleic acid or maleic anhydride and acrylic acid, an N-methyl fatty acid (optionally C.sub.8-C.sub.18)-sarcosinate, a carboxylic acid optionally a resin acid or a fatty acid (optionally C.sub.8-C.sub.18) or a salt of optionally carboxylic acid, and the salts of these copolymers, d. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates and the sodium salts of dioctylsulfosuccinic acid, e. at least one inert filler selected from the group consisting of carbonates, silicates and oxides, and also urea-formaldehyde condensates and celluloses, f. at least one structure former selected from the group consisting of polyacrylic acid and salts thereof, crosslinked polyacrylates and polyureas, polyurethanes and derivatized polyureas and polyurethanes, g. at least one complexing agent selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), glutaconic acid, nitrilotriacetic acid, diethylenediaminepentaacetic acid, and salts and/or hydrates thereof, h. optionally one or more further active insecticidal ingredients, i. optionally one or more further adjuvants.

14. Composition according to claim 1, comprising the compound having formula (I-2) having the following structure: ##STR00042## (I) b. at least one inorganic basic ammonium salt selected from the group consisting of diammonium hydrogensulfate (DAHP), c. at least one dispersant selected from the group consisting of sodium salts of copolymers of methacrylic acid and styrene, d. at least one anionic wetting agent selected from the group consisting of the sodium salts of alkylated naphthalenesulfonates, e. at least one inert filler selected from the group comprising kaolin, rutile and silicon dioxide, f. at least one structure former selected from the group consisting of polymethylurea resins, g. at least one complexing agent selected from the group consisting of EDTA and the salts and hydrates thereof, optionally a tetrasodium salt, h. optionally one or more further active insecticidal ingredients, i. optionally one or more further adjuvants.

15. Composition according to claim 1, wherein components a-g are present as follows: a) 4-8% by weight b) 60-66% by weight c) 8-12% by weight d) 1.5-2.5% by weight e) 10-22% by weight f) 3-8% by weight g) 0.1-1% by weight.

16. Composition according to claim 1, wherein component h) is present as follows: h) 10-35% by weight.

17. Composition according to claim 1, wherein component i) is present as follows: i) 0.1-5% by weight.

18. Process for producing a composition according to claim 1, comprising mixing components and then extruding.

19. Product comprising a composition according to claim 1 for application of one or more active agrochemical ingredients to one or more plants and/or a habitat thereof.

20. Product comprising a content of a composition according to claim 1.

21. Product comprising a composition according to claim 1 for controlling one or more insects.

Description

EXAMPLES

1. Suspendability

1.a) Suspendability of a Solo Formulation

[0172] To achieve good suspendability at high salt concentration in the formulation, the following dispersing aids were tested as follows:

[0173] 20 g of a mixture of 0.96 g of compound I-2, 13 g of diammonium hydrogenphosphate (DAHP), 0.4 g of Morwet EFW (wetting agent), 1 g of Pergopak M, 0.1 g of Trilon B Powder, 2.54 g of Kaolin W and 2 g of dispersing aid were ground in an IKA A 10 analysis mill (20 000 rpm) for 2 min and tested for gravimetric suspendability.

TABLE-US-00006 Visual Suspendability, Dispersing aid assessment initial Agrilan 789 Dry good 99.1 Geropon Ultrasperse good 98.2 Tersperse 2700 good 98.1 Atlox Metasperse 550 S good 98.0 Narlex D-72 good 98.0 Geropon TA/72 good 98.8 Versa-TL3 good 97.6 Geropon T36 good 96.7 Tersperse 2020 good 73.4/81 Supragil MNS/90 good/sediment 72.1 Borresperse CA good/sediment 88 Rhodacal BX78 flocculates readily 87.2 Reax 88B flocculates 72.6 Polyfon O flocculates 70.3

Determination of Suspendability

[0174] A 1% suspension in water (CIPAC C) is dispersed in a 250 ml measuring cylinder. The mixture is equilibrated for 30 minutes. Subsequently, the upper 9/10 of the suspension is removed. The remaining 1/10 is dried and the residue is determined gravimetrically. Suspendability is defined as:

10/9*100*(amount of sample [g]*proportion a.i. [%]/100−residue [g])/(amount of sample [g]*proportion a.i. [%]/100)

[0175] Thus, a value of 100% corresponds to a homogeneous distribution of all insoluble constituents throughout the sample volume.

[0176] A good visual assessment means no sediment and no flocculation.

1.b) Suspendability and Stability of Solo & Mixed Formulation Suspendability experiments on solo and mixed formulation after storage at elevated temperature.

[0177] 1 kg of a mixture of compound 1-2 (different in example 12), optionally a second active ingredient, diammonium hydrogenphosphate (DAHP), Morwet EFW, Pergopak M, optionally Trilon B Powder, Kaolin W, dispersing aid and defoamer, in the manner known to the person skilled in the art, is ground in a Hosokawa 100 AS 4″ air-jet mill (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g/min), moistened with water (about 14% by weight) and extruded using a Fuji Paudal dome extruder (die size 0.8 mm) to give a WG, and dried further in a fluidized bed dryer.

TABLE-US-00007 Sample 1 1a 2 3 4 5 6 6a 7 8 8a 9 10 11 12 I-2 [g] 48 48 48 24 18 18 36 24 24 18 24 18 48 48 0.72 Ethiprole/[g] 300 150 150 300 300 Flupyradifurone/[g] 100 150 150 150 DAHP/[g] 650 650 650 300 521 521 353 365 500 456 440 456 650 650 9.75 Morwet EFW/[g] 20 20 20 20 20 20 20 20 20 20 20 20 20 20 0.3 Pergopak M/[g] 50 50 50 50 50 50 50 50 50 50 50 50 50 50 0.75 Trilon B Powder/[g] 5 5 5 20 5 5 5 5 5 5 5 5 5 5 ( ) Kaolin W/[g] 127 117 127 136 136 136 136 126 201 201 201 201 127 127 1.76 Tersperse 2700/[g] 100 100 150 100 100 100 100 100 100 1.5 Atlox Metasperse 550 100 100 100 S/[g] Versa-TL 3/[g] 100 Agrilan 789 Dry/[g] 100 Rhodorsil Antimousse 10 10 10 EP 6703 Visual assessment good good good good good good good good good good good good good good good Suspend., init./[%] 98.8 98.2 98.2 99.0 97.6 98.0 97.7 97 94.1 97.4 96.4 96.7 98.2 98.7 98.4 Suspend. 2W 54° C./ 99.3 98.3 98.7 98.9 97.8 97.5 97.5 96.5 97.4 97.2 96.5 96.9 kA kA kA [%]

2. Producibility

2.a) Experiments on the Granulation Method

[0178] Preparation of a WG by means of extrusion as a suitable granulation method by lower thermal stress.

[0179] a) A mixture of COMPOUND 1-2, a second active ingredient, diammonium hydrogenphosphate (DAHP), Morwet EFW, Pergopak M, Trilon B Powder, Kaolin W and dispersing aid, in the manner known to the person skilled in the art, is ground in a Hosokawa 100 AS 4″ air-jet mill (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g/min), moistened with water (about 14% by weight) and extruded using a Fuji Paudal dome extruder (die size 1 mm) to give a WG, and dried further in a fluidized bed dryer.

[0180] b) A mixture of COMPOUND 1-2, DAHP, Geropon T36, Geropon SDS, Trilon B Powder and Reax 88A is dispersed in water to give a 50% slurry, ground in the manner known to the person skilled in the art with a bead mill and then dried by means of spray drying (Niro SD 6.3 spray dryer) or by means of a fluidized bed granulator (Niro Aeromatic MP1).

TABLE-US-00008 14 15 Sample 13 (comparative) (comparative) Compound I-2/[g] 48 1200 48 DAHP/[g] 600 18112.5 744.5 Morwet EFW/[g] 20 Geropon T 36/[g] 125 5 Geropon SDS/[g] 62.5 2.5 Pergopak M/[g] 50 Trilon B Powder/[g] 20 500 Kaolin W/[g] 162 Tersperse 2700/[g] 100 Reax 88 A/[g] 5000 200 Reax 88 B/[g] Production method Extrusion Spray drying Fluidized bed pH of 1% dispersion 7.7 6.7 6.7

[0181] By means of spray drying or fluidized bed, the pH of the spray liquor falls too far (<7).

2.b) Optimization of the Extrudability of the WG

[0182] A mixture of COMPOUND 1-2, a second active ingredient, Morwet EFW, Pergopak M, optionally Trilon B Powder, Tersperse 2700, DAHP and optionally Kaolin W, in the manner known to the person skilled in the art, is ground in a Hosokawa 100 AS 4″ air-jet mill (injector air 5.5 bar, grinding air 4.5 bar, throughput 100 g/min), moistened with water (about 14% by weight) and extruded using a Fuji Paudal dome extruder (die size 0.8 or 1 mm) to give a WG, and dried further in a fluidized bed dryer.

TABLE-US-00009 Sample 18 = 20 21 22 = 23 16 17 12 19 (comparative) (comparative) 3 (comparative) 24 147/[g] 48 48 48 48 48 48 24 24 24 Ethiprole/[g] 300 Flupyradifurone/ 100 100 [g] DAHP/[g] 500 550 600 650 700 762 300 500 300 Morwet EFW/ 20 20 20 20 20 20 20 20 20 [g] Pergopak M/[g] 50 50 50 50 50 50 50 50 50 Trilon B Powder/ 20 20 20 20 20 20 20 5 [g] Kaolin W/[g] 282 212 162 112 62 136 136 351 Tersperse 2700/ 100 100 100 100 100 100 150 150 150 [g] Process extr. extr. extr. extr. extr. extr. extr. extr. extr. Assessment good good good good poor no good no good extrudate extrudate pH of 1% 7.7 7.6 7.7 7.7 7.7 — 7.4 — 7.5 dispersion

[0183] As apparent from comparative examples 20 and 21, no extrudates or no extrudates in adequate quality can be obtained in the case of an insufficient amount of filler or too great an amount of salt.

[0184] Example 22 shows that the optimal content of filler has to be adjusted in the case of an active ingredient combination.

3) Solubility of the Active Ingredient

[0185] Attempts to increase the availability of the active ingredient in the spray liquor by improving the solubility as a function of the amount of salt. [0186] 6 samples of sample 19 (see example 2b) were dispersed in 50 g of water, such that concentrations of 0.12 or 0.24 g of active ingredient/l were achieved. The mixtures were stirred and, in each case after 30 min, 2 h and 5 h, centrifuged completely, and the proportion of dissolved active ingredient in the supernatant was determined by means of HPLC.

TABLE-US-00010 30 min 2 hours 5 hours 0.12 g of active 91.2% 94.6% 96.2% ingredient/l 0.24 g of active 87.5% 92.1% 98.3% ingredient/l [0187] There is virtually complete solubility of the active ingredient in the spray liquor only by virtue of the formulations according to the invention.

4) Bioavailability

[0188] Measurement of Penetration into the Plant [0189] In this test, the penetration of active ingredients though enzymatically isolated cuticles of apple tree leaves was measured. [0190] Leaves which had been cut off in the fully developed state from apple trees of the Golden Delicious variety were used. The cuticles were isolated by [0191] first filling leaf discs that had been marked with dye on the underside and punched out with a pectinase solution (0.2% to 2%) buffered to a pH between 3 and 4 by means of vacuum infiltration, [0192] then adding sodium azide and [0193] then leaving the leaf discs thus treated to stand until dissolution of the original leaf structure and until the detachment of the noncellular cuticle. [0194] Thereafter, only the cuticles of the upper leaf sides which were free of stomata and hairs were used in the further procedure. They were repeatedly washed alternately with water and a buffer solution of pH 7. The clean cuticles obtained were finally applied to Teflon sheets and smoothed and dried with a gentle air stream. [0195] In the next step, the cuticle membranes thus obtained were placed into stainless steel diffusion cells (=transport chambers) for membrane transport studies. For this purpose, the cuticles were positioned using tweezers centrally onto the edges of the diffusion cells which had been smeared with silicone grease and sealed with a ring which had likewise been greased. The arrangement was selected such that the morphological outer side of the cuticles was directed outward, i.e. toward the air, while the original inner side faced the interior of the diffusion cell. [0196] The diffusion cells were filled with a 30% ethylene glycol/water solution. To determine the penetration, 10 μl in each case of a spray liquor of the composition below were applied to the outside of the cuticle. The spray liquor was made up with local tap water of moderate water hardness. [0197] After the application of the spray liquors, the water was allowed to evaporate, the chambers were inverted and they were placed in thermostatted tanks in which the temperature and air humidity above the cuticle were adjustable via a gentle air flow onto the cuticle bearing the spray deposit (20° C., 60% rh). Aliquots were taken by an autosampler at regular intervals and the active ingredient content was determined by HPLC. [0198] The experimental results are shown in the table below. The numbers reported are average values from 8 to 10 measurements. [0199] Sample 1 and a comparative sample (sample 25) with the same concentration of ammonium dihydrogenphosphate (ADHP) rather than DAHP were analysed. [0200] Application rate 0.1 g a.i./l, +3 g/l RME, temperature 30° C., air humidity 56%, stirring time 24 h

TABLE-US-00011 pH 0 h 12 h 24 h Sample 1 7.8 0% 72% 79% Sample 25 6.5 0% 23% 37% (comparative) [0201] As sample 25 shows, at a pH<7, penetration of the active ingredient/bioavailability is no longer sufficient, or these are distinctly lowered. The pH and hence the use of a basic salt and thus has a crucial effect on AI penetration.

Materials Used

[0202] Kraftsperse® EDF-350, ® DD-5, Kraftsperse® DD-8, Kraftsperse® DW-8, Kraftsperse® EDF-450, Reax® 88B and Reax® 907 are lignosulfonates from Ingevity, North Charleston, S.C., USA.

[0203] Geropon® TA/72, T/36 is a polycarboxylic acid sodium salt from Solvay.

[0204] Oparyl® MT 804 is a dibutylnaphthalenesulfonic acid sodium salt from Giovanni Bozzetto S.p.A., Filago, Italy.

[0205] Oparyl® DT 530 is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt from Giovanni Bozzetto S.p.A., Filago, Italy. Pergopak® M is a polymethylurea resin from Albemarle Corporation, Baton Rouge, La., USA.

[0206] Rhodorsil® EP 6703 is a polydimethylsiloxane on starch from Rhodia, Boulogne, France.

[0207] Celite® 209 S is a diatomaceous earth from Lehmann & Voss, Hamburg, Germany.

[0208] Luzenac 2 talc is a magnesium hydrosilicate from Luzenac Europe, Paris, France.

[0209] Kaolin W is an aluminium hydrosilicate from Erbslöh Lohrheim GmbH & Co. KG, Lohrheim, Germany.

[0210] Borresperse® Na and Ufoxane® 3 A are lignosulfonates from Borregaard, Sarpsborg, Norway.

[0211] Morwet® D 425 is a naphthalenesulfonic acid-formaldehyde condensate, sodium salt from Akzo Nobel, Stenungsund, Sweden.

[0212] Tersperse® a is naphthalenesulfonic acid-formaldehyde condensate, sodium salt from Huntsman, The Woodlands, Tex., USA.

[0213] Baykanol® SL is an alkylarylsulfonate from Lanxess, Leverkusen, Germany.

[0214] Rhodorsil Antimousse EP 6703® is an absorbed polydimethylsiloxane, Solvay.