FORMULATION OF INSECTICIDAL MIXTURES COMPRISING GLYCOL ETHER SOLVENTS

Abstract

The invention relates to insecticidal active ingredient formulations comprising at least one dissolved active ingredient and one active ingredient in solid form having good storage stability at high and low temperatures and high active ingredient penetration, to a process for production thereof and to the use thereof for application of the active ingredients present.

Claims

1 Composition comprising: a) at least one active ingredient solid at room temperature, b) at least one active ingredient soluble in an organic solvent other than a), c) at least one ammonium salt, d) at least one dispersant comprising a alkyl propoxylate ethoxylate, e) optionally one or more surfactants, f) at least one water-insoluble filler, g) at least a solvent selected from compounds represented by formula 4, wherein ##STR00035## y=1-9 A,B=H, or linear C1-C4-Alkyl, independent from each other, and M=H, or C1-C2-Alkyl; with the exception of 1,2-propylene glycol which is explicitly excluded from the definition according to g). and h) optionally one or more further adjuvants, where active ingredient a) is insoluble or only sparingly soluble in the chosen solvent g).

2. The composition according to claim 1, wherein component e) is obligatory.

3. The composition according to claim 1, wherein a) is selected from the group of the active insecticidal ingredients having a solubility in the chosen solvent g) of not more than 5 g/l, optionally not more than 4 g/l, optionally not more than 2.5 g/l, and optionally not more than 1 g/l.

4. The composition according to claim 1, wherein a) is selected from the group comprising diamide insecticides, spinosyns (IRAC Group 5), mectins (IRAC Group 6), ethiprole, triflumuron, deltamethrin, thiacloprid and tetronic acid or tetramic acid derivatives (IRAC Group 23).

5. The composition according to claim 1, wherein a) is selected from the group of the tetronic acid or tetramic acid derivatives (IRAC Group 23).

6. The composition according to claim 1, wherein a) is a tetramic acid derivative of formula (I) ##STR00036## 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 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 ##STR00037## 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.

7. The composition according to claim 1, wherein component a) is a compound of formula (I-2) ##STR00038##

8. The composition according to claim 1, wherein b) is selected from the group of insecticides comprising nAChR agonists, flonicamid and 4-[[(6-chloropyridin-3-yl)methyl](3-fluoro-n-propyl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-1-yl)amino]furan-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino]furan-2(5H)-one, (E/Z)-4-[[(6-chloropyridin-3-yl)methyl](2-fluorovinyl)amino]-5-methylfuran-2(5H)-one, 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]-5-methylfuran-2(5H)-one, 3-bromo-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, 3-chloro-4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, and 4-[methyl[(6-chloropyridin-3-yl)methyl](am ino)]furan-2(5H)-one.

9. The composition according to claim 1, wherein b) is selected from the group consisting of imidacloprid, clothianidin, flupyradifurone, flonicamid and acetamiprid.

10. The composition according to claim 1, wherein b) is flupyradifurone.

11. The composition according to claim 1, wherein c) is selected from the group comprising ammonium carbonate, ammonium hydrogensulfate, ammonium sulfate (AMS), ammonium hydrogencarbonate, ammonium carbonate and diammonium hydrogen-phosphate (DAHP).

12. The composition according to claim 1, wherein d) is selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compound of formula (III-a)
R—O-A-B—H   (III-a) where R is a C1-C4 fragment, optionally a C3-C4 fragment, optionally a C4 fragment, A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), optionally consisting of 15-35 PO units, optionally consisting of 20-30 PO units, B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units (formula Ill-c) together with 0-10 propylene glycol (PO) units, optionally consisting of 20-40 EO units together with 0-8 PO units, optionally consisting of 30-40 EO units together with 0-5 PO units, ##STR00039## and alkyl polypropylene glycol-polyethylene glycol compounds of formula (IIId)
R—O—(C.sub.mH.sub.2mO).sub.x—(C.sub.nH.sub.2nO).sub.y—R′  (IIId) in which R and R′ are independently hydrogen, a linear C.sub.1- to C.sub.5-alkyl radical or a branched C.sub.3- or C.sub.4-alkyl radical; m is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, where one radical n or m has the meaning of 2 and the other radical n or m has the meaning of 3.

13. The composition according to claim 1, wherein e) is a surfactant selected from the group comprising polycarboxylate types, salts of sulfated formaldehyde condensation products with alkylaromatics, salts of sulfated formaldehyde condensation products with ditolyl ether, salts of sulfated formaldehyde condensation products with cyclohexanone, and lignosulfonates and salts thereof.

14. The composition according to claim 1, wherein f) is selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silicas, attapulgites and fillers based on synthetic polymers.

15. The composition according to claim 1, wherein g) is selected from a solvent represented by formula 4, wherein ##STR00040## y=1-3 A,B=H, or linear C1-C4-Alkyl, independent from each other, and M=H, or C1-C2-Alkyl; with the exception of 1,2-propylene glycol which is explicitly excluded from the definition according to g).

16. The composition according to claim 1, wherein the components are present as follows: a) 1-30% by weight b) 1-20% by weight c) 1-40% by weight d) 1-40% by weight e) 0-10% by weight f) 0.1-15% by weight h) 1-20% by weight g) to one litre.

17. The composition according to claim 1, wherein the components are present as follows: a) 2-15% by weight b) 1-12% by weight c) 15-30% by weight d) 10-30% by weight e) 0.5-2.5% by weight f) 1-10% by weight h) 2.5-17.5% by weight g) to one litre.

18. The composition according to claim 1, comprising a) compound having formula (I-2) having the following structure: ##STR00041## b) flupyradifuron, c) at least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogenphosphate (DAHP), d) at least one dispersant selected from the group comprising alkyl polypropylene glycol-polyethylene glycol compound of formula (III-a)
R—O-A-B—H   (III-a) where R is a C1-C4 fragment, optionally a C3-C4 fragment, optionally a C4 fragment, A is a polypropylene glycol fragment consisting of 10 to 40 propylene oxide (PO) units (formula III-b), optionally consisting of 15-35 PO units, optionally consisting of 20-30 PO units, B is a randomly copolymerized polyethylene glycol-polypropylene glycol fragment consisting of 10-50 ethylene oxide (EO) units (formula Ill-c) together with 0-10 propylene glycol (PO) units, optionally consisting of 20-40 EO units together with 0-8 PO units, optionally consisting of 30-40 EO units together with 0-5 PO units, ##STR00042## and alkyl polypropylene glycol-polyethylene glycol compounds of formula (IIId)
R—O—(C.sub.mH.sub.2mO).sub.x—(C.sub.nH.sub.2nO).sub.y—R′  (IIId) in which the individual radicals and indices have the following definitions: R and R′ are independently hydrogen, a linear C.sub.1- to C.sub.5-alkyl radical or a branched C.sub.3- or C.sub.4-alkyl radical; TABLE-US-00021 M is 2 or 3; n is 2 or 3; x is 5 to 150; and y is 5 to 150, where one radical n or m has the meaning of 2 and the other radical n or m has the meaning of 3, e) at least one surfactant comprising a polycarboxylate, f) at least one filler selected from the group comprising fumed silicas and attapulgites, g) is selected from the group comprising dipropylene glycol monomethyl ether, 1-methoxy-2-propanol and dipropylene glycol, and h) optionally one or more further adjuvants.

19. A product according to claim 1 for controlling insects.

Description

EXAMPLE I

[0451] All formulation constituents according to the experiments described in Table I are combined in a suitable vessel and homogenized while stirring. Subsequently, bead grinding is conducted (e.g. Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding) until a particle size of 10-15μ is reached (determination by microscopy). The resultant formulation is analysed by means of e.g. suspension stability and rotational viscosity. Subsequently, a storage test is conducted at elevated temperature and then a quantitative assessment of phase separation after storage.

TABLE-US-00015 TABLE 1 (figures in grams per L) example # I-1* I-2* I-3* I-4 Compound I-2 12 12 12 12 Flupyradifurone 75 75 75 75 DAHP 250 250 250 250 Aerosil R812S 30 30 30 30 SAG 1572 0.5 0.5 0.5 0.5 Geropon T/36 10 10 10 10 Morwet D-425 10 10 10 10 Antarox B/848 200 200 200 200 Dowanol DPM to vol. (~532.5) Dowanol PM to vol. (~512.5) Propylene glycol to vol. (~572.5) Dipropylene glycol to vol. (~562.5) particle appearance ~5-10 μm ~5-10 μm ~10-15μ >15μ (microscopy) rotational viscosity 333.0 290.0 1520.0 1726.0 @ 7.5 1/s [mPa*s] suspension stability at DoM: 0.0 0.0 0.0 n.t. sediment after 1 h [mL] Supernatant after 2 w 20° C. [%] 0.0 5.0 0.0 n.t suspension stability 2 w 20° C.: <0.10 <0.10 <0.10 n.t. sediment after 1 h [mL] Supernatant after 2 w 54° C. [%] 6.0 6.0 0.0 n.t. suspension stability 2 w 54° C.: <0.10 <0.10 <0.10 n.t. sediment after 1 h [mL] Supernatant after 2 w 40° C. [%] 2.0 5.0 0.0 n.t. Supernatant after 2 w temp. 0.0 0.0 0.0 n.t. cycling [%] *examples according to invention. DAHP = Diammoniumhydrogenphosphate; DOM = Day of Manufacturing

[0452] Discussion: As depicted in Table I, formulations prepared according to example I-1 to I-3 exhibit suitable particle sizes and excellent suspension stability together with a low to medium viscosity and very low phase separation after storage for 2 weeks at different conditions. The formulation prepared according to example I-4 exhibits a high viscosity combined with coarse particles and is thus not according to the invention. In this case the preparation of a sample with smaller particle size was not pursued due to the build-up of high viscosity already after milling for some minutes upon which the milling process was stopped.

EXAMPLE II

[0453] All formulation constituents according to the experiments described in Table II are combined in a suitable vessel and homogenized while stirring. Subsequently, bead grinding is conducted (e.g. Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding) until a particle size of 10-15μ is reached (determination by microscopy). The resultant formulation is analysed by means of e.g. suspension stability, rotational viscosity and Rheology (determination of phase angle, G′ and G″). Subsequently, a storage test is conducted at elevated temperature and then a quantitative assessment of phase separation after storage is done.

TABLE-US-00016 TABLE II (figures in grams per L) Example # II-1* II-2 II-3* II-4* II-5* II-6 II-7 II-8* II-9* Compound I-2 12 12 12 12 12 12 12 12 12 Flupyradifurone 75 75 75 75 75 75 75 75 75 DAHP 250 250 250 250 250 250 250 250 250 Aerosil R812S 40 40 40 40 35 30 35 35 40 SAG 1572 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Geropon T/36 10 10 10 10 10 10 10 10 10 Morwet D-425 10 10 10 10 10 10 10 10 10 Antarox B/848 200 200 200 200 200 200 200 200 200 Propylene glycol 80.5 170 80 279.5 259.5 Dipropylene glycol to vol. 262.5 (~352.5) Dowanol DPM to vol. to vol. to vol. (~452) (~372.5) (~312.5) Dowanol PM 200 to vol. to vol. to vol. to vol. 175 to vol. (~502.5) (~439.5) (~283) (~260) (~260) *inventive example; DAHP = Diammoniumhydrogenphosphate

[0454] Discussion:

TABLE-US-00017 Example # II-1* II-2 II-3* II-4* II-5* II-6 II-7 II-8* II-9* rotational viscosity 709 1191 596 663 634 827 1508 632 1096 @ 7.5 1/s [mPa*s] Phase Angle [°] 19.9 19.7 20.6 17.8 22.9 19.1 19.6 31.8 19.9 G′ Elastic Modulus 73.9 125.2 47.68 69.8 59.84 207.7 371.5 21.76 104 [Pa] G″ Viscous 26.8 44.8 17.9 22.4 25.27 72.08 132.2 13.5 37.5 Modulus [Pa] suspension stability 0.0 0.5 0.0 0.0 0.0 0.0 0.0 at DoM: sediment after 1 h [mL] supernatant after 3.0 0 0 0.0 0.0 4 w 20° C. [%] supernatant after 5.0 3 2 14.0 2.0 4 w 40° C. [%] supernatant after 8 w 2.0 0.0 temp.- cycling [%] supernatant after 12.0 5.0 8 w@40° C. [%] supernatant after 0.0 4.0 1.0 3.0 6.0 16 w@20° C. [%] supernatant after 10.0 2.0 9.0 5.0 5.0 16 w@40° C. [%] *inventive example; DoM = Day of Manufacturing

[0455] All formulations according to the invention exhibit viscosities below or around 1000 mPa*s @ 7,5 1/s which can be considered of practical usefulness (Table 1, examples II-1; II-3 to II-5; II-8; II-9). All examples exhibit small phase angles at or around 30° which attributes to a good storage stability. However, all examples according to the invention exhibit an elastic Modulus G′ of around or below 100 Pa and a corresponding viscous Modulus G″ which is significantly below G′. With regard to phase separation, all formulations according to the invention exhibit no or only low levels of supernatant after 4, 8 or 16 weeks of storage at either 20° C./roomtemp, 40° C. or temp. cycling. Thus, after storage at 40° C. for 8 or 16 weeks, respectively, a maximum of phase separation between 0-10% was observed. Formulations that contain large amounts of propylene glycol exhibit higher viscosities and/or higher level of supernatant up to 14% (Table I, examples II-2; II-6; II-7) and are therefore not according to the invention.

EXAMPLE III

[0456] For the purpose of testing different levels of carrier fluids g), adjuvants h) and water-insoluble filler f) all formulation constituents according to the experiments described in Table III are combined in a suitable vessel and homogenized while stirring. Subsequently, bead grinding is conducted (e.g. Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding) until a particle size of 10-15μ is reached (determination by microscopy). The resultant formulation is analysed by means of suspension stability, rotational viscosity and Rheology. Subsequently, a storage test is conducted at elevated temperature and then a quantitative assessment of suspension stability after storage is performed.

TABLE-US-00018 TABLE 3 (figures in gram per L) Example No. III-1* III-2* III-3 III-4 III-5 Compound I-2 12 12 12 12 12 Flupyradifurone 75 75 75 75 75 DAHP 250 250 250 250 250 SAG1572 0.5 1 0.5 0.5 0.5 Geropon T36 10 10 10 10 10 Morwet D-425 10 10 10 10 10 Antarox B/848 200 200 200 200 200 Propylenglycol 80 120 160 200 240 Aerosil R812S 40 40 40 40 40 Dowanol DPM to volume to volume to volume to volume to volume (~432.5) (422.5) (~362.5) (~322.5) (~292.5) d(max) after preparation [μm] 12.0 10.0 12.0 12.0 12.0 rotational viscosity [mPa*s] @ 1017 992.0 1325 1518 2234 7.5 1/s Phase Angle [°] 18 n.t 20.5 17.9 15.5 G′ Elastic Modulus [Pa] 108.9 n.t 98.5 158 288 G″ Viscous Modulus [Pa] 35.4 n.t 36.8 51.6 79.9 suspension stability at DoM: 1.0 0.0 1.0 0.0 0.0 sediment after 1 h [mL] suspension stability 1 w 54° C.: 0.0 0.0.sup.# 8.0 10.0 10.0 sediment after 1 h [mL] suspension stability 1 w 20° C.: 0.0 0.0.sup.# 8.0 0.0 0.0 sediment after 1 h [mL] *inventive example; DAHP = Diammoniumhydrogenphosphate; .sup.#determined after 2 weeks

[0457] Discussion: Formulations prepared according to example III-1 and III-2 exhibit a medium viscosity and and a good suspension stability even after storage; moreover, example III-1 exhibits a small phase angle, an elastic Modulus G′ of around or below 100 Pa together with a corresponding viscous Modulus G″ which is significantly below G′. Thus, III-1 and III-2 are examples according to the invention.

[0458] Formulations prepared according to example III-3 are slightly higher in viscosity and exhibit a similar G′ compared to III-1 which can be attributed to the increased amount of propylene glycol in this recipe. Formulations prepared according to example III-4 and III-5 exhibit an increasing and high viscosity and elastic Modulus G′ which can again be attributed to the increased amount of propylene glycol in this recipe.

EXAMPLE IV

[0459] For the purpose of testing different combinations of at least one active ingredient solid at room temperature a) with at least one active ingredient b) while keeping the formulation recipe unchanged, suitable active ingredients were selected as specified in Table IV, combined and homogenized while stirring. Subsequently, bead grinding is conducted (Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding for 40 min) and the resultant formulation is analysed by means of e.g. suspension stability, rotational viscosity and particle size assessment. Subsequently, a storage test is conducted at elevated temperature and samples were furthermore assessed including the determination of phase separation after storage.

TABLE-US-00019 TABLE IV (figures in gram per L) Example # IV-1* IV-2* IV-3* IV-4* IV-5* IV-6* IV-7* IV-8* Flupyradifurone 75 75 75 75 75 75 Acetamiprid 50 Flonicamid 50 Compund I-2 25 50 25 Tetraniliprole 50 Cyantraniliprole 50 Ethiprole 50 Spirotetramat 50 Thiacloprid 50 DAHP 250 250 250 250 250 250 250 250 Aerosil R812S 40 40 40 40 40 40 40 30 SAG 1572 1 1 1 1 1 1 1 1 Geropon T/36 10 10 10 10 10 10 10 10 Morwet D-425 10 10 10 10 10 10 10 10 Antarox B/848 200 200 200 200 200 200 200 200 Propylene glycol 120 120 120 120 120 120 120 80 Dowanol DPM to vol. to vol. to vol. to vol. to vol. to vol. to vol. To vol. (~384) (~384) (~384) (~384) (~384) (~434) (~384) (~484) rotational viscosity 1440.0 1205.0 1170.0 945.0 848.0 686.0 1176.0 356.0 @ 7.5 1/s [mPa*s] d90 [μm] at DoM 5.58 5.39 5.97 5.38 3.91 3.48 6.02 5.63 d90 [μm] after 5.63 5.5 6.03 8.53 3.93 3.52 6.29 n/a storage 2 w 54° C. d90 [μm] after 5.74 5.5 6.08 5.52 3.99 3.64 6.27 n/a storage 2 w 20° C. Supernatant after 1.0 2.0 1.0 1.0 0.0 1.0 2.0 5.0 2 w 54° C. [%] Supernatant after 0.0 0.0 0.0 0.0 0.0 0.0 0.0 5.0 2 w 20° C. [%] Supernatant after 2 w 0.0 0.0 0.0 0.0 0.0 0.0 0.0 n/a temp. cycling [%] suspension stability at 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 DoM: sediment after 1 h [mL] suspension stability 2 w 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 54° C.: sediment after 1 h [mL] suspension stability 2 w 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 20° C.: sediment after 1 h [mL] *inventive example; DAHP = Diammoniumhydrogenphosphate; DoM = Day of Manufacturing

[0460] Discussion: Examples IV-1 to IV-7 exhibit a rotational viscosity between 850 and 1500 mPa*s at 7.5 l/s combined with a particle size d90 of between 3 to 6 μm (Malvern result) and excellent suspension stabilities after lh. After storage for 2 weeks hardly any phase separation was detected and only marginal changes in particle size are visible (exemption is example IV-4 where some crystal growth is visible after storage at 54° C.) which indicates stable formulations that are according to the invention. Moreover, suspension stabilities after storage are continuously good and even excellent in some cases.

EXAMPLE V

[0461] Cuticle penetration by flupyradifurone and compound I-2

[0462] Experimental procedure:

[0463] This test measures the penetration of active ingredients through enzymatically isolated cuticles of apple tree leaves.

[0464] Leaves that have been cut off apple trees in the developed state and isolated by the method described in Schönherr and Riederer (Schönherr, J., Riederer, M. (1986)) are used. Only the cuticles of the top sides of the leaves that are free of stomata and hair are used further.

[0465] For membrane transport studies, the cuticular membranes thus obtained are placed into stainless steel diffusion cells (=transport chambers). For this purpose, the cuticles are placed with tweezers onto the middle of the silicone grease-smeared edges of the diffusion cells and sealed with a likewise greased ring. The arrangement is chosen such that the morphological outside of the cuticles is directed outward, i.e. toward the air, while the original inside faces the inside of the diffusion cell. The diffusion cells are filled with water or with a mixture of water and solvent and buffered to the physiologically relevant pH of 5.5. The medium in the diffusion cells is supposed to simulate the apoplast, i.e. the natural absorption medium within the leaf. This method is of good suitability for systemic and mechanistic studies with the aim of understanding the effect of the formulations, adjuvants and solvents on penetration of the crop protection compositions.

[0466] To determine the penetration, 5 μl in each case of a spray liquor containing the active ingredients Flupyradifurone and I-1 in specified formulations (cf. Table V) hereinafter are applied to the outside of a cuticle. The active ingredient concentration corresponds to the field application rate customary in practice. For preparation of the spray liquor the corresponding ingredients in the given amounts are given into tap water and homogenized by mixing.

[0467] After the spray liquors have been applied, the water is allowed to evaporate in each case, then the chambers are inverted and they are placed into thermostated tanks, wherein air at a defined air humidity and temperature is blown onto the outside of the cuticles in each case. The penetration that sets in therefore takes place at a relative air humidity of 56% and a set temperature of 25° C. At regular intervals, an autosampler is used to take samples and the content of penetrated active ingredient is measured by means of HPLC. The numbers reported are average values from 5 to 10 individual measurements in each case.

TABLE-US-00020 TABLE V Penetration test results Amount [g/L] present in aqueous spray solution Penetration after 24 h [%] Compd Antarox Compd # I-2 Flupyradifurone Solvent 1.sup.§ Solvent 2.sup.§ B/848 DAHP* Flupyradifurone I-2 1 0.1 0.5 5.1 0 2 0.1 0.5 1.6 29.2 11.9 3 0.1 0.5 1.3 73 28.6 4 0.1 0.5 1.3 1.6 82.8 90.1 5 0.1 0.5 1.8 (B) 1.8 (C) 1.3 1.6 87.2 55 6 0.1 0.5 1.8 (B) 1.8 (D) 1.3 1.6 100 70 7 0.1 0.5 2.1 (A) 1.4 (B) 1.3 1.6 100 65 8 0.1 0.5 2.5 (A) 1.2 (C) 1.3 1.6 95 61 *DAHP = Diammoniumhydrogenphosphat, .sup.$A = Dipropylenglycolmonomethylether, B = Propylenglycolmonomethylether, C = Propylenglycol, D = Dipropylenglycol

[0468] Evaluation of the Experiments:

[0469] The two active substances tested, flupyradifurone and I-2, on their own show barely any, if any, cuticle penetration either when employed without additives (Table V, entry 1). The applications of active ingredients in the presence of diammoniumhydrogenphosphate (DAHP) and especially Antarox B/848 independently lead to an improvement in cuticle penetration for both active ingredients tested (Table V entries 2-3). As soon as Antarox B/848 and DAHP are used in combination, the maximum penetration potential is found, which is the additive combination of the individual effects for both active ingredients in the formulation (Table V, entry 4). In the presence of different solvent combinations (Table V, entries 5-8) together with a combination of Antarox B/848 and DAHP a very similar effect can be observed; while Flupyradifurone exhibits increased penetration behaviour the penetration of I-2 is slightly reduced, albeit still on a very high level and certainly better than with Antarox B/848 or DAHP alone.