HIGHLY LOADED FORMULATIONS WITH INSECTICIDES OF THE KETOENOL CLASS FOR USE IN DRIP AND DRENCH APPLICATIONS

Abstract

The present invention relates to solvent-free aqueous suspension concentrates having high active ingredient concentration, good biological efficacy and good rheological stability, and to processes for production thereof. The formulations of the invention are suitable for the field of plant protection.

Claims

1. A composition comprising: a. at least one ketoenol insecticide b. at least one dispersant, optionally selected from the group of the nonionic dispersants and salts thereof, c. at least one pH buffer, d. at least one rheology modifier, e. optionally at least one antifreeze, f. optionally at least one biocide, g. optionally at least one defoamer, and h. optionally further active ingredients and adjuvants, and i. water.

2. The composition according to claim 1, wherein a) is a tetramic acid derivative of formula (I) ##STR00026## 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 they are bonded are C3-C6-cycloalkyl substituted by an optionally C1-C4-alkyl- or C1-C4-alkoxy-C1-C2-alkyl-substituted alkylenedioxy group that forms a 5-membered or 6-membered ketal together with the carbon atom to which it is bonded, G is hydrogen (a) or is one of the groups ##STR00027## 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.

3. The composition according to claim 1, wherein component a) is a compound of formula (I) ##STR00028## with TABLE-US-00014 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

4. The composition according to claim 1, wherein component a) is a compound of formula (I-2) ##STR00035##

5. The composition according to claim 1, wherein component b) is a nonionic dispersant based on one or more tristyrylphenol polyethylene glycol ethers.

6. The composition according to claim 1, wherein component c) is citrate- or phosphate-based pH buffer.

7. The composition according to claim 1, wherein xanthan is used as rheology modifier component d).

8. The composition according to claim 1, wherein component e) is an antifreeze selected from the group consisting of ureas, diols and polyols.

9. The composition according to claim 1, wherein component f) is a biocide selected from the group of the isothiazolinones.

10. The composition according to claim 1, wherein component g) is a silicone-based defoamer.

11. The composition according to claim 1, wherein components a-d are present as follows: a) 200-400 g/L b) 40-90 g/L, c) 0.9-2.0 g/L, d) 3-5 g/L.

12. The composition according to claim 1, wherein components a-g are present as follows: a) 200-400 g/L b) 40-90 g/L, c) 0.9-2.0 g/L, d) 3-5 g/L, e) 100-150 g/L, f) 0.05-1.5 g/L, g) 0.05-1.5 g/L.

13. The composition according to claim 1, comprising a. compound of formula (I) ##STR00036## where the compound of formula (I) have the following definitions: W is methyl, X is chlorine or methyl, Y is chlorine, bromine or methyl, A, B and the carbon atom to which they are attached represent saturated C6-cycloalkyl which is substituted by an alkylenedioxy group which, together with the carbon atom to which it is attached, forms a 5-membered or 6-membered ketal, G is hydrogen (a) or is one of the groups ##STR00037##  in which M is oxygen, E is one metal ion equivalent or an ammonium ion, R1 is straight-chain or branched C1-C4-alkyl, R2 is straight-chain or branched C1-C4-alkyl. (I) b. at least one nonionic dispersant selected from the group consisting of tristyrylphenol alkoxylates and fatty acid polyglycol ether esters, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. at least one rheology modifier consisting of the group comprising organic thickeners based on xanthan or cellulose or a combination thereof, e. optionally at least one antifreeze selected from the group consisting of ureas, diols and polyols, f. optionally at least one biocide from the group of isothiazolinones, g. optionally at least one defoamer from the group of the silicone- or silane-based defoamers, h. optionally further active ingredients and adjuvants.

14. The composition according to claim 1, comprising a. compound having formula (I-2) having the following structure: ##STR00038## b. at least one nonionic dispersant selected from the group consisting of tristyrylphenol alkoxylates, c. at least one pH buffer selected from the group consisting of citrate- and phosphate-based pH buffers, d. at least one rheology modifier selected from the group comprising xanthan, e. optionally at least one antifreeze selected from the group consisting of ethylene glycol and propylene glycol, glycerol, optionally propylene glycol or glycerol, more optionally glycerol, f. optionally at least one biocide selected from the group consisting of benzisothiazolinone, g. optionally at least one defoamer from the group of the silicone-based defoamers, h. optionally further active ingredients and adjuvants.

15. A product comprising a content of a composition according to claim 1.

16. The product of claim 15 for controlling insects.

Description

EXAMPLES

Feedstocks Used:

[0216] The terms used in the examples below have the following meanings:

TABLE-US-00007 citric acid polybasic organic acid Rhodopol ® 23 xanthan derivative (Solvay) Silfoam ® SRE silicone defoamer (Wacker) SAG 1572 silicone defoamer (Momentive) glycerol antifreeze Proxel ® GXL preservative (biocide, Proxel) Kathon CG/ICP preservative (biocide, Rohm and Haas) Lucramul PS29 tristyrylphenol ethoxylate (dispersant, Levaco) Lucramul PS54 tristyrylphenol ethoxylate (dispersant, Levaco) Atlox 4913 ethoxylate polymethacrylate graft (dispersant, Croda)

Preparation Examples

[0217] To prepare a suspension concentrate, all liquid components are first mixed with one another. In the next step, the solids are added and stirred until a homogeneous suspension is obtained. The homogeneous suspension is subjected first to a coarse and then to a fine grinding operation, so as to obtain a suspension in which 90% of the solid particles have a particle size below 5 μm. Subsequently added while stirring at room temperature are the preliminary thickener solution, antifreeze and water. A homogeneous suspension concentrate is obtained.

[0218] The examples which follow illustrate the invention without limiting it in any way. All figures are in g/L.

TABLE-US-00008 TABLE 3 Comparative examples Disper- Rheology pH Anti- Bio- sant modifier buffer freeze cide Defoamer Water 1-1 1-2 25 40 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL 1-2 1-2 49 15/45 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL 1-3 1-2 100 40 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL 1-4 1-2 100 15/45 1.2 1 Glycerol 100 0.8/1.2 1 Water R ad 1000 mL est 1-5 1-2 200 15/45 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL 1-6 1-2 300 15/45 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL 1-7 1-2 400 15/45 1.2 1 Glycerol 100 0.8/1.2 1 Water ad 1000 mL

TABLE-US-00009 TABLE 4 Inventive examples Disper- Rheology pH Anti- Bio- sant modifier buffer freeze cide Defoamer Water 2-1 I-2 100 42 4 1 Glycerol 106 0.8/ 1 Water ad 1000 1.2 mL 2-2 I-2 100 16/ 4 1 Glycerol 106 Kathon 0.8/ 1 Water ad 1000 48 CGI/ 1.2 mL Proxel GXL 2-3 I-2 200 16/ 4 1 Glycerol 109 0.8/ 1 Water ad 1000 49 1.2 mL 2-4 I-2 300 17/ 4 1 Glycerol 112 0.8/ 1 Water ad 1000 51 1.2 mL 2-5 I-2 400 17/ 5 1 Glycerol 114 0.8/ 1 Water ad 1000 51 1.2 mL 2-6 I-2 100 42 4.24 7.4 Glycerol 106 0.85/ 1 Water ad 1000 5.9 1.27 mL 2-7 I-2 100 42 4.2 7.4 Glycerol 106 0.85/ 1 Glycerol ad 1000 30.7 1.27 mL 2-8 I-2 225 16.4/ 4.4 0 Glycerol 109 — 0.87/ SAG1572 1 Water ad 1000 47.7 1.31 mL

TABLE-US-00010 TABLE 5 Rheological properties (Comparative) Dynamic Viscosity example @ Yield Stress (Pa*s) 1-1 50° 0.1 0.5 (comparative) 1-2 50° 0.1 0.4 (comparative) 1-3 45° 0.1 0.5 (comparative) 1-4 45° 0.1 0.5 (comparative) 1-5 40° 0.1 1 (comparative) 1-6 30° 0.02 10 (comparative) 1-7 15° 0.05 50 (comparative) 2-1 25° 2 12 2-2 25° 1 10 2-3 25° 2 13 2-4 20° 3 30 2-5 15° 0.2 400 2-6 20° 3 29 2-7 20° 3 30 2-8 8 + 0.1 25° 3 20

[0219] As table 5 shows, the formulations of the invention have improved rheological properties with a lower tendency to sedimentation and clumping. This is apparent both from the greater modulus of elasticity of the formulations of the invention and the smaller phase angle.

[0220] Accordingly, the formulations of the invention have higher yield stress and higher dynamic viscosity at the yield point than the formulations known from the prior art.

[0221] Technical characterization and storage stability

[0222] The dispersions do not lose their rheological properties on storage over 2W@RT/30° C./54° C. (table 2).

TABLE-US-00011 TABLE 6 Rheological Properties & Storage Stability Modulus of Phase angle elasticity (Pa) @ (°) @ Dynamic under stress under stress viscosity (measured @ (measured @ Yield @yield 0.1 Hz) 0.1 Hz) stress stress (Pa*s) 2-1 8 Pa 8/8 Pa 25° 25°/25° 2 2/1 12 12/10 @0.2 @0.2 2-2 5 Pa 5/5 Pa 25° 30°/30° 1 3/3 10 10 @0.1 @0.1 2-3 15 Pa 12/10 Pa 25° 25°/27° 2 2/2 13 10/6  @0.1 @0.1 2-4 35 Pa 7/6 Pa 20° 20°/25° 3  10/7   30 4/3 @0.005 @0.6 2-5 80 Pa 80/60 Pa 15° 15°/20° 0.2 0.5/0.2 400 400/300 @0.003 @0.003 2-6 8 Pa @3 8/8 Pa 20° 20°/20° 4   4/4   29 21/21 @3 2-7 8 Pa @3 8/8 Pa 20° 20°/20° 3   3/3.6 30 25/19 @3 2-8 8 @0.1 8/6Pa 25° 25°/35° 3 3/2 20 20/10 @0.1

[0223] In addition, the representative formulation example 2-8 does not lose its technical properties (AI concentration, particle size, syneresis) after storage (table 7).

TABLE-US-00012 TABLE 7 Technical Properties & Storage Stability Al Syneresis Particle size concentration of sediment/ (d90/d50 μm) (% w/w) (% separation) 2W 8W 2W 8W 2W 8W Forum RT/ RT/ RT/ RT/ RT/ RT/5 Start 54 54 Start 54 54 Start 54 4 2-8 3/1 2.3/ 2.5/ 21.6 21.4/ 21.4/ 0 0/0 0/0 0.6; 0.7; 21/6 21.6 2.6/ 2.7/ 0.7 0.8 indicates data missing or illegible when filed

[0224] Unless defined otherwise, W means weeks and D means days in the context of the present invention.

Biological Activity after Drip Application

[0225] Drip application in greenhouse test: Cotton plants are planted in flowerpots with 1 L of sandy loam soil (58.5% sand, 12.9% clay, 28.5% loam, 1.6% humus, pH 6.8). After 7 days, 1 mg of the active ingredient in the specified formulation in 60 mL of water is dripped into the soil in the pot about 1 cm from the stem of the plant using a soil spike over a period of 15 min. The plants are kept in a greenhouse at 25° C. under adequate illumination. Infection with a mixed population of Aphis gossypii follows after a further seven days (in which the plants are watered as required without water overtopping the pot). 7 days after the infection, mortality (dead animals compared to a fully effective standard and to the untreated control) is evaluated.

[0226] Drench application in greenhouse test: Cotton plants are planted in flowerpots with 1 L of sandy loam soil (58.5% sand, 12.9% clay, 28.5% loam, 1.6% humus, pH 6.8). After 7 days, 2 mg of the active ingredient in the specified formulation in 60 mL is poured all at once into the soil in the pot around the stem. The plants are kept in a greenhouse at 25° C. under adequate illumination. Infection with a mixed population of Aphis gossypii follows after a further seven days (in which the plants are watered as required without water overtopping the pot). 7 days after the infection, mortality (dead animals compared to a fully effective standard and to the untreated control) is evaluated.

TABLE-US-00013 TABLE 8 Application Formulation AI pH of spray Biological method example concentration solution control Drip 2-8 1 mg AI/L 55% soil pH 7 65% Drench 2-8 2 mg AI/L pH 5 85% soil pH 7 93%

Test and Storage Methods:

[0227] All tests were conducted by CIPAC methods that are customary in crop protection (CIPAC=

[0228] Collaborative International Pesticides Analytical Council; www.cipac.org). Long-term storage was conducted according to CIPAC MT 46.3 at room temperature/54° C. for a storage time of 2 weeks. The terms used hereinafter have the following meanings: Unless stated otherwise, testing is conducted in a 1% solution in water (CIPAC D, water hardness 342 ppm) at 23° C. [0229] 0T=test result after zero days of storage; [0230] 2W RT/54=test result of the accelerated storage test (2 weeks at room temperature/54° C.) to test the long-term stability of a formulation product; [0231] D90/50=active ingredient particle size (laser scattering, 90%/50% of all volume particles); [0232] D90/50 2WRT/54=active ingredient particle size after storage test (2 weeks at room temperature/54° C.); an increase in the values indicates crystal growth, with an increase by a factor of 2 usually still being acceptable; more than a factor of 4 is unacceptable; [0233] Sediment=values>10% indicate significant sediment formation.