OIL-BASED SUSPENSION CONCENTRATES

Abstract

Novel oil-based suspension concentrates consisting of at least one room temperature-solid compound of the formula (I), at least one suspended ammonium salt of the formula (1), at least one mineral oil, vegetable oil, fatty acid triglyceride or fatty acid alkyl ester, at least one nonionic surfactant and/or at least one anionic surfactant, optionally an uptake promoter, and optionally one or more additives from the groups of the spreaders, the foam inhibitors, the antioxidants, the dyes and/or the thickeners.
a process for producing these suspension concentrates and the use thereof for application of the active ingredients present.

Claims

1. An oil-based suspension concentrate comprising at least one room temperature-solid compound of formula (I) ##STR00015## in which W and Y are independently hydrogen, C.sub.1-C.sub.4-alkyl, chlorine, bromine, iodine or fluorine, X is C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, chlorine, bromine or iodine, D is hydrogen or methyl, A, B and the carbon atom to which A, B are bonded are C.sub.3-C.sub.6-cycloalkyl in which one ring member has optionally been replaced by nitrogen and which is optionally monosubstituted by C.sub.1-C.sub.4-alkoxy, A, B and the carbon atom to which they are bonded are C.sub.3-C.sub.6-cycloalkyl substituted by an optionally C.sub.1-C.sub.4-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 it is bonded, G is hydrogen (a) or is one of the groups ##STR00016## in which E is a metal ion or an ammonium ion, M is oxygen or sulfur, R.sup.1 is straight-chain or branched C.sub.1-C.sub.6-alkyl, R.sup.2 is straight-chain or branched C.sub.1-C.sub.6-alkyl and at least one suspended ammonium salt of formula (1) ##STR00017## in which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen or in each case optionally mono- or polysubstituted C.sub.1-C.sub.8-alkyl or C.sub.1-C.sub.8-alkylene, where the substituents may be selected from halogen, nitro and cyano, n is 1, 2 or 3, R.sup.5 is hydrogencarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulfate, tartrate, sulfate, nitrate, thiosulfate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate, citrate, oxalate, carbonate, pentaborate, sulfite, benzoate, hydrogenoxalate, hydrogencitrate, methylsulfate or tetrafluoroborate, at least one mineral oil, vegetable oil, fatty acid triglyceride or fatty acid alkyl ester, at least one nonionic surfactant and/or at least one anionic surfactant, optionally an uptake promoter, and optionally one or more additives from the groups of the spreaders, the foam inhibitors, the antioxidants, the dyes and/or the thickeners.

2. The oil-based suspension concentrate as claimed in claim 1, wherein W is methyl, X is chlorine or methyl, Y is chlorine, bromine or methyl, D is hydrogen, A, B and the carbon atom to which they are bonded are saturated C.sub.6-cycloalkyl substituted by an 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 ##STR00018## 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.1 is straight-chain or branched C.sub.1-C.sub.4-alkyl.

3. The oil-based suspension concentrate as claimed in claim 1, wherein the substituents W, X, Y, A, B, D and G have the definitions given in the table: TABLE-US-00021 (I) W X Y A B G D CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 CH.sub.3 Cl H H CH.sub.3 CH.sub.3 Br H H CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 CH.sub.3 Cl H H CH.sub.3 CH.sub.3 Br H H

4. The oil-based suspension concentrate as claimed in claim 1, wherein the compound of formula (I) has the following structure: ##STR00026##

5. A process for producing the suspension concentrate as claimed in claim 1, comprising mixing at least one room temperature-solid compound of formula (I), at least one ammonium salt of formula (1), at least one mineral oil, vegetable oil, fatty acid triglyceride or fatty acid alkyl ester, at least one nonionic surfactant and/or at least one anionic surfactant, optionally an uptake promoter, and optionally one or more additives from the groups of the spreaders, the foam inhibitors, the antioxidants, the dyes and/or the thickeners with one another, and then optionally grinding the resulting suspension.

6. The suspension concentrate as claimed in claim 1, wherein the ammonium salt of formula (1) used is ammonium sulfate.

7. The suspension concentrate as claimed in claim 1, wherein the ammonium salt of formula (1) used is diammonium monohydrogenphosphate.

8. The suspension concentrate as claimed in claim 1, wherein rapeseed oil methyl ester is present.

9. The suspension concentrate as claimed in claim 1, wherein caprylic acid/capric acid triglyceride is present.

10. The suspension concentrate as claimed in claim 1, wherein the uptake promoter present is at least one alkanol alkoxylate of formula
R—O—(-AO).sub.m-R′  (II) in which R is straight-chain or branched alkyl having 4 to 20 carbon atoms, R′ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl or n-hexyl, AO represents an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and m represents numbers from 2 to 30.

11. The suspension concentrate as claimed in claim 1, wherein the content of compound of formula (I) is between 0.5% and 20% by weight, of ammonium salt of formula (1) is between 5-35% by weight, of oil is between 20-75% by weight, of nonionic surfactant and/or anionic surfactant is 1-25% by weight, of uptake promoter is between 0-25% by weight, of additives is between 0-10% by weight.

12. A product comprising one or more suspension concentrates as claimed in claim 1 for application of the compounds of formula (I) present to one or more plants and/or a habitat thereof.

13. A product comprising one or more suspension concentrates as claimed in claim 1 for control of insects.

14. A composition comprising a content of a suspension concentrate as claimed in claim 1 and one or more extenders and/or surface-active reagents.

Description

PREPARATION EXAMPLES

Comparative Example

[0150] 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 10 μm. Subsequently, Kelzan® S and water are added while stirring at room temperature to attain the defined viscosity. A homogeneous suspension concentrate is obtained.

TABLE-US-00002 49 g of the compound of the formula (I-2) 15 g Soprophor ® TS 54 45 g Atlox ® 4913 100 g glycerol 1 g citric acid 1 g Silfoam ® SRE 1.2 g Proxel ® GXL 0.8 g Preventol ® D7 1.2 g Kelzan ® S 785.8 g water

Example 1 (OD 006)

[0151] To prepare an oil-based suspension concentrate,

TABLE-US-00003 5.7 g of the compound of the formula (I-2) 297 g ammonium sulfate.sup.1 57 g Tanemul 1371 A 50 g ATLOX 4914 44 g Tanemul SO 70 1.5 g SIPERNAT 22 S
are added while stirring at room temperature to .sup.1For optimal comminution of the suspension, the ammonium sulfate is precomminuted by means of an airjet mill.

TABLE-US-00004 544.8 g Edenor MESU.

[0152] After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

Example 2 (OD 012)

[0153] To prepare an oil-based suspension concentrate,

TABLE-US-00005 11.5 g of the compound of the formula (I-2) 245 g ammonium sulfate.sup.1 58 g Tanemul 1371 A 49 g ATLOX 4914 46 g Tanemul SO 70 2.5 g SIPERNAT 22 S
are added while stirring at room temperature to

TABLE-US-00006 588 g Edenor MESU.

[0154] After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

Example 3 (OD 048)

[0155] To prepare an oil-based suspension concentrate,

TABLE-US-00007 48 g of the compound of the formula (I-2) 262.5 g ammonium sulfate.sup.1 56.7 g Tanemul 1371 A 52.5 g ATLOX 4914 48.3 g Tanemul SO 70 1.5 g SIPERNAT 22 S
are added while stirring at room temperature to

TABLE-US-00008 582 g Edenor MESU.
gegeben. After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

Example 4 (OD 024)

[0156] To prepare an oil-based suspension concentrate,

TABLE-US-00009 24 g of the compound of the formula (I-2) 262.5 g ammonium sulfate.sup.1 56.5 g Tanemul 1371 A 52.5 g ATLOX 4914 48.3 g Tanemul SO 70 1.5 g SIPERNAT 22 S
are added while stirring at room temperature to

TABLE-US-00010 605.4 g Edenor MESU.

[0157] After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

Example 5 (OD 024)

[0158] To prepare an oil-based suspension concentrate,

TABLE-US-00011 24 g of the compound of the formula (I-2) 200 g diammonium hydrogenphosphate.sup.1 90 g RHODAFAC MB 60 g RHODACAL 60 BE 40 g LUCRAMUL SO 21 15 g SIPERNAT 22 S 10 g MORWET D-425
are added while stirring at room temperature to

TABLE-US-00012 551 g Phytorob 926.65.

[0159] After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

Example 6 (OD 024)

[0160] To prepare an oil-based suspension concentrate,

TABLE-US-00013 24 g of the compound of the formula (I-2) 100 g ETOCAS 10 50 g ATLOX 4914 40 g TWEEN 85 15 g SIPERNAT 22 S 5 g BORRESPERSE NA 2 g 2,6-di-tert-butyl-4-methylphenol
are added while stirring at room temperature to

TABLE-US-00014 614 g Miglyol 812 N.

[0161] After addition has ended, the mixture is stirred at room temperature for a further 10 minutes. The resultant 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 7 μm.

TABLE-US-00015 Substance Chem. Material name designation Manufacturer CAS No. type Soprophor ® Ethoxylated Solvay 104376-75-2 Nonionic TS 54 Tristyrylphenol surfactant Atlox ® 4913 Ethoxylated Croda 119724-54-8 Nonionic polymethacrylate polymer graft polymer Glycerol Glycerol various 56-81-5 Antifreeze Citric acid Citric acid various 77-92-9 Silfoam ® SRE Polydimethylsiloxane Wacker 69011-36-5 Defoamer preparation Proxel ® GXL Aqueous dipropylene Arch 2634-33-5 Biocide glycol solution of ~20% Chemical 1,2-benzisothiazolin-3-one as sodium salt Preventol ® D7 1.5% mix of LanXess 55965-84-9 Biocide 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin- 3-one Kelzan ® S Xanthan Gum CP Kelco 11138-66-2 Thickener Tanemul 1371 A Calcium Levaco 26264-06-2 Anionic dodecylbenzenesulfonate (Tanatex) surfactant (CaDBS) in n-butanol ATLOX 4914 ethoxylated nonionic Croda n/a Nonionic random polymer surfactant Tanemul SO 70; Ethoxylated soybean oil; Levaco 61791-23-9 Nonionic Lucramul SO21 fatty acid polyethylene (Tanatex) surfactant glycol ether ester SIPERNAT 22 S Precipitated amorphous Evonik 112926-00-8 Thickener silica Edenor MESU; Fatty acids, C16-18 and various 67762-38-3 Oil Phytorob C18-unsaturated, Me 926.65 esters RHODACAL Calcium Solvay 26264-06-2 Anionic 60 BE dodecylbenzenesulfonate surfactant (CaDBS) in 2-ethylhexanol MORWET naphthalenesulfonate Akzo 9008-63-3; Anionic D-425 formaldehyde condensate Nobel 68425-94-5 surfactant sodium salt RHODAFAC Tridecyl alcohol Solvay 9046-01-9 Nonionic MB ethoxylate phosphate 3EO surfactant ETOCAS 10 Castor oil, ethoxylated, Akzo 61791-12-6 Nonionic 10EO Nobel surfactant Miglyol Caprylic/capric Sasol 65381-09-1; Oil 812 N triglycerides (C8/10) 73398-61-5 TWEEN 85 SORBITAN TRIOLEATE Croda 9005-70-3 Nonionic 20 EO surfactant BORRESPERSE Lignosulfonic acid, Borregaard 8061-51-6 Anionic NA sodium salt surfactant

BIOLOGICAL EXAMPLES

Example 1

[0162] Myzus persicae Test (MYZUPE Translaminar)

[0163] To prepare an appropriate application solution, 1 part by weight of formulation is mixed with water to the desired concentration. In the event that addition of ammonium salts or ammonium salts and penetrants is required, these are each pipetted into the final preparation solution at a concentration of 1000 ppm after dilution.

[0164] One-leaved bell pepper plants (Capsicum annuum) heavily infested by the green peach aphid (Myzus persicae) are treated by spraying the top side of the leaf with the active ingredient formulation in the desired concentration.

[0165] After the desired time, the kill in % is determined. 100% means that all the animals have been killed; 0% means that no animals have been killed.

[0166] In this test, for example, the following compounds from the preparation examples show good efficacy at an application rate of 100 L/ha:

TABLE-US-00016 % kill rate Animal 2 d after Active ingredient g a.i./ha species application Ex. (I-2) 12 MYZUPE 55 SC 050 + RME + AMS 6 MYZUPE 40 Ex. (I-2) 12 MYZUPE 65 OD 006 6 MYZUPE 60

Example 2

[0167] Aphis gossypii Test (APHIGO Translaminar)

[0168] To prepare an appropriate application solution, 1 part by weight of formulation is mixed with water to the desired concentration. In the event that addition of ammonium salts or ammonium salts and penetrants is required, these are each pipetted into the final preparation solution at a concentration of 1000 ppm after dilution.

[0169] One-leaved cotton plants (Gossypium hirsutum) heavily infested by the cotton aphid (Aphis gossypii) are treated by spraying the top side of the leaf with the active ingredient formulation in the desired concentration.

[0170] After the desired time, the kill in % is determined. 100% means that all the animals have been killed; 0% means that no animals have been killed.

[0171] In this test, for example, the following compounds from the preparation examples show good efficacy at an application rate of 300 L/ha:

TABLE-US-00017 % kill rate Animal 7 d after Active ingredient g a.i./ha species application Ex. (I-2) 3 APHIGO 90 SC 050 + RME + AMS 1.5 APHIGO 85 0.75 APHIGO 60 Ex. (I-2) 3 APHIGO 98 OD 006 1.5 APHIGO 93 0.75 APHIGO 80 RME = rapeseed oil methyl ester AMS = ammonium sulfate

Example 3

[0172] About 10 m.sup.2 aubergine plots (about 40 cm in size) are treated for Bemisia tabaci in triplicate. Application is effected with a compressed air-operated backpack sprayer. The active ingredient from example (I-2) as OD 012 is tested here in the specified application rates in comparison with an SC 050 which is deployed in a tankmix with 0.1% a.i. rapeseed oil methyl ester (500 EW) and 0.1% a.i. ammonium sulfate. The water application rate is 750 L/ha.

[0173] Evaluation is effected 1, 7, 14 and 21 days by counting the living animals. Subsequently, efficacy in percent is calculated according to Henderson and Tilton.

TABLE-US-00018 Active ingredient (I-2) Application rate Efficacy (% H + T) Formulation (g) a.i./ha 1 d 7 d 14 d 21 d SC 050 12 60 81.9 100 78.3 OD 012 12 62.2 92.2 100 80.7

Example 4

[0174] Cabbage plots of about 10 m.sup.2 in size are treated for Myzus persicae in quadruplicate. Application is effected with a compressed air-operated backpack sprayer. The active ingredient from example (I-2) as OD 012 is tested here in the specified application rates in comparison with an SC 050 which is deployed in a tankmix with 0.1% a.i. rapeseed oil methyl ester (500 EW) and 0.1% a.i. ammonium sulfate. The water application rate is 750 L/ha.

[0175] Evaluation is effected 3, 5, 7, 10 and 15 days after treatment by scoring the animal kill rate on the leaves.

TABLE-US-00019 Active ingredient (I-2) Application rate Efficacy (% Abbott) Formulation (g) a.i./ha 3 d 5 d 7 d 10 d 15 d SC 050 6 66 83 82 95 100 OD 012 6 81 88 99 100 100

Example 5

[0176] Cabbage plots of about 10 m.sup.2 in size are treated for Brevicoryne brassicae in triplicate. Application is effected with a compressed air-operated backpack sprayer. The active ingredient from example (I-2) as OD 012 is tested here in the specified application rates in comparison with an SC 050 which is deployed in a tankmix with 0.1% a.i. rapeseed oil methyl ester (500 EW) and 0.1% a.i. ammonium sulfate. Two applications are made with an interval of 14 days at a water application rate of 500 L/ha.

[0177] Evaluation is effected 7, 14 and 21 days after the second treatment by scoring the animal kill rate on the leaves.

TABLE-US-00020 Active ingredient (I-2) Application rate Efficacy (% Abbott) Formulation (g) a.i./ha 7 d 14 d 21 d SC 050 12 93 85 100 OD 012 12 100 90 100