FORMULATION OF INSECTICIDES COMPRISING GLYCOL ETHER SOLVENTS

Abstract

The invention relates to insecticidal active ingredient formulations comprising at least one active ingredient or a combination of active ingredients 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. A Composition comprising: a) at least one active ingredient solid at room temperature, b) at least one ammonium salt, c) at least one dispersant comprising an alkyl propoxylate ethoxylate, d) optionally one or more surfactants, e) at least one water-insoluble filler, f) at least one solvent selected from compounds represented by formula 4, wherein ##STR00040## y=1-9 A,B=H, or linear Alkyl M=H, or Alkyl and g) optionally one or more further adjuvants, wherein active ingredient a) is insoluble or only slightly soluble in the chosen solvent f), and wherein e) is selected from the group comprising modified natural silicates, silicate minerals, synthetic silicates and fumed silicas, attapulgites and fillers based on synthetic polymers.

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

3. The composition according to claim 1, wherein a) is selected from the group of active insecticidal ingredients having a solubility in the chosen solvent f) 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, beta-cyfluthrin, deltamethrin 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) ##STR00041## wherein 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 ##STR00042## wherein 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 a) is a compound of formula (I-2) ##STR00043##

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

9. The composition according to claim 1, wherein c) 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 III-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, ##STR00044## 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) wherein R and R′ are independently hydrogen, a linear C1- to C5-alkyl radical or a branched C3- or C4-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.

10. The composition according to claim 1, wherein d) 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.

11. The composition according to claim 1, wherein f) is selected from a solvent represented by formula 4, wherein ##STR00045## y=1-3 A,B=H, or linear Alkyl M=H, or Alkyl

12. The composition according to claim 1, wherein the components are present as follows: a) 0.5-30% by weight b) 1-40% by weight c) 0.5-40% by weight d) 0-10% by weight e) 0.1-10% by weight g) 0-20% by weight f) to one litre.

13. The composition according to claim 1, wherein the components are present as follows: a) 1-20% by weight b) 5-35% by weight c) 5-35% by weight d) 0.3-8% by weight e) 0.5-10% by weight g) 1-20% by weight f) to one litre.

14. The composition according to claim 1, comprising a) compound having formula (I-2) having the following structure: ##STR00046## b) at least one ammonium salt selected from the group comprising ammonium sulfate (AMS) and diammonium hydrogenphosphate (DAHP), c) 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 III-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, ##STR00047## 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) wherein the individual radicals and indices have the following definitions: R and R′ are independently hydrogen, a linear C1- 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, d) at least one surfactant selected from the group comprising polycarboxylate types, e) at least one filler selected from the group comprising fumed silicas and attapulgites, f) at least one solvent selected from compounds represented by formula 4, wherein ##STR00048## y=1-2 if A=H, then B=Methyl, and if A=Methyl, then B=H M=H, or Methyl g) optionally one or more further adjuvants.

15. A product comprising a composition according to claim 1 for controlling insects.

Description

EXAMPLE I

[0464] All formulation constituents according to the experiments described in Tables Ia-c are combined in a 25 ml PE screwtop bottle, and 10 g of glass beads (size 1-1.25 mm) are added. The bottle is closed, clamped in an agitator apparatus (Retsch MM301) and treated at 30 Hz for 40 minutes; in the course of this, the samples heat up. After the time has elapsed, the samples are cooled down to room temperature and the consistency of the formulation is assessed. Subsequently, by means of a microscope (Zeiss transmitted light microscope, 40-fold magnification), the particle size is determined by laser dispersion and the dispersion is assessed for its properties. A very small particle size indicates good grindability, while the presence of agglomerates is a sign of poor dispersion characteristics.

TABLE-US-00010 TABLE 1 (figures in % by weight) Example No. 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 I-2 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 SAG 1572 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 DAHP [% w/w] 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 AMS [% w/w] 20.00 20.00 20.00 Geropon T36 1.00 5.00 1.00 1.00 1.00 1.00 1.00 Morwet D-425 5.00 1.00 1.00 1.00 1.00 1.00 Soprophor 3D33 5.00 Soprophor FLK 5.00 Rhodacal 60 BE 5.00 Borresperse NA 5.00 Emulsogen EL 400 5.00 Antarox B/848 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Atlas G5002L 20.00 20.00 Lucramul HOT 5902 20.00 20.00 Dipropylene Glycol 56.90 52.90 52.90 52.90 52.90 52.90 52.90 52.90 57.90 55.90 55.90 55.90 55.90 55.90 Monomethyl Ether (Dowanol DPM) Concentrate fluid fluid fluid fluid fluid highly fluid fluid highly fluid fluid fluid fluid fluid viscous viscous Particle size [d90/50, 3.9/ 3.0/ 5.6/ 51/ 10/ not 6.8/ 425/ not 314/ 3.8/ 2.2/ 3.3/ 2.4/ μm] 1.5 1.5 2.3 2.6 3.7 possible 2.2 14 possible 4.7 1.7 1.1 1.6 1.0 Agglomerates [yes/no] yes no yes yes yes yes no yes yes no some no no no

[0465] Evaluation of the Experiments:

[0466] The formulations based on I-2, ammonium salt and Dowanol DPM with different amounts of surfactants (experiment 1-1, 1-2) show basic grindability of the respective ammonium salts and of I-2 under the experimental conditions specified, but significant agglomeration of the salt crystals in the concentrate is observed under the microscope, unless sufficient surfactant (>1%) is present in the formulation, meaning that the individual particles are dispersed very inadequately, if at all, in the liquid phase. Only certain surfactants are able to properly disperse the ammonium salt and I-2 (e.g. 1-2, 1-7), and alkyl propoxylate ethoxylates are not able to do this on their own, as can be seen by the highly viscous nature of the sample milled only with Antarox B/848 (1-9), as well as the presence of the agglomerates.

[0467] Most effective and surprising is the combination of two different surfactants in small amounts (experiments 1-10 to 1-14). This combination (Geropon T-36 and Morwet D-425) is particularly surprising because 1.00% of each surfactant is more most effective in milling and stabilizing DAHP or AMS, than 5.00% of each of the surfactants alone.

EXAMPLE II

[0468] For the purpose of testing suitable thickeners and carriers in the presence of suitable dispersing aids, all formulation constituents as specified in Table 2, in Table 3, and in Table 4 are combined and are milled by one of the below mentioned methods: [0469] 1) Formulation components are homogenized with a colloidal mill, and subsequently, milled in a bead mill (Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding for 40 min). After the time has elapsed, the samples are cooled down to room temperature and the rheological properties of the formulation are assessed. [0470] 2) Formulation components are mixed in a bottle, which is then closed, clamped in an agitator apparatus (Retsch MM301) and treated at 30 Hz for 40 minutes; in the course of this, the samples heat up. After the time has elapsed, the samples are cooled down to room temperature and the rheological properties of the formulation are assessed.

[0471] The rheological properties of the formulation were assessed with a Gemini Rheometer (Bohlin Instruments). The measurement of G′ (elastic modulus), G″ (viscous modulus) and Phase Angle are measured at different frequencies (between 0.01-5 Hz) at room temperature using a frequency sweep routine with either strain or stress control. The assessment of viscosity is performed at room temperature as per the CIPAC MT192; “Viscosity of Liquids by rotational viscometry” method.

TABLE-US-00011 TABLE 2 (figures in % w/w) Example No. 2-1 2-2 2-3 2-4 2-5 2-6 I-2 2.40 2.40 2.40 2.40 2.40 2.40 SAG 1572 0.10 0.10 0.10 0.10 0.10 0.10 DAHP 25.00 25.00 25.00 25.00 25.00 25.00 Geropon T36 1.00 0.81 0.81 0.81 0.81 0.81 Morwet D-425 1.00 0.81 0.81 0.81 0.81 0.81 Antarox B/848 20.00 20.00 20.00 20.00 20.00 20.00 Aerosil 380 4.00 Aerosil R812S 4.00 Aerosil R805 4.00 Aerosil R972 4.00 Aerosil R106 4.00 Aerosil R 202 4.00 Propylene Glycol 15.00 15.00 15.00 15.00 15.00 15.00 Dipropylene Glycol To 100% To 100% To 100% To 100% To 100% To 100% Monomethyl Ether (Dowanol DPM) Dynamic viscosity @ 1552/573 665/398 2622/921 1104/365 955/304 Not possible shear rate 24/s, 108/s to mill due (mPas) at room to very high temperature viscosity G′ @ 0.5 Hz (Pa) 182 440 133 39 11 at room temperature G″ @ 0.5 Hz (Pa) 288 238 234 48 18 at room temperature Phase Angle @ 0.5 Hz 58 28 60 51 60 (°) at room temperature

[0472] Evaluation of the Experiments in Table 2:

[0473] Formulations using Aerosil R812 S (Example No. 2-2) are the only ones with a low Phase angle, this showing that these formulations have a much higher elastic character, and are thus expected to be more stable with respect to sedimentation stability. Additionally, the sedimentation stability of Example 2-2 comes without the high viscosity observed for the other examples, which have much higher dynamic viscosities than example 2-2 at the low shear rate 1/24.

TABLE-US-00012 TABLE 3 (figures in % by weight) Example No. 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-11 I-2 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 SAG 1572 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 DAHP 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 Geropon T36 1.00 1.00 1.00 1.00 1.00 0.81 0.81 0.81 0.81 0.81 0.81 Morwet D-425 1.00 1.00 1.00 1.00 1.00 0.81 0.81 0.81 0.81 0.81 0.81 Antarox B/848 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Aerosil R812S 4.00 4.00 4.00 4.00 4.00 2.00 2.00 2.00 2.00 2.00 2.00 Propylene Glycol 5.00 15.00 15.00 15.00 15.00 15.00 Dipropylene Glycol 10.00 Glycerin 10.00 Dipropylene Glycol To To To Monomethyl Ether 100% 100% 100% (Dowanol DPM) 1-methoxy-2-propanol To (Dowanol PM) 100% Diethylene Glycol To Monomethyl Ether 100% (Methyl Carbitol) PEG 400 To To 100% 100% Tripropylene glycol To To monomethyl ether 100% 100% (Dowanol TPM) Dipropylene glycol To To monopropyl ether 100% 100% (Dowanol DPNP) Dynamic Viscosity @ 382/246 634/347 1314 (@20/s)/ 440/248 932(@20/s)/ 4087/ 128/125 288/231 95/90 244/187 114/73 shear rate 24/s, 108/s 537(@100/s) 396(@100/s) 1304 (mPas) at room temperature G′ @ 0.5 Hz (Pa) at 75 50 405 174 258 7121 0.06 9 0.5 14 94 room temperature G″ @ 0.5 Hz (Pa) 32 25 96 60 83 12820 0.49 7 0.7 9 39 at room temperature Phase Angle @ 0.5 Hz 23 26 13 19 18 61 82 39 52 34 23 (°) at room temperature

[0474] Evaluation of the Experiments in Table 3:

[0475] Formulations using dipropylene glycol monomethyl ether (Examples 3-1, 3-2, 3-3) all show very good rheological properties, namely high elasticity (low phase angle<30°), and shear thinning properties. The formulations containing propylene glycol (Example 3-1) or dipropylene glycol (Example 3-2) have also a relatively low viscosity at low shear rates (<700 mPas @24/s). Other carriers such as 1-methoxy-2-propanol (Exp. 3-4) or diethylene glycol monomethyl ether (Exp. 3-5) also give formulations with low phase angles and in the case of Exp. 3-4 relatively low viscosities at low shear rates. PEG 400 does not yield processable formulations due a very high viscosity (Expt 3-6), but this can be improved by the addition of some propylene glycol (Expt. 3-11), whereby the formulation becomes much more elastic (Phase angle 23° @0.5 Hz), and much more tractable in terms of viscosity (114 mPas @ 24 Hz). Neither tripropylene glycol monomethyl ether (Expt 3-7) nor dipropylene glycol monopropyl ether (Expt 3-9) induce enough elasticity in the formulation so as to expect a stable product towards sedimentation. This can be seen in the very high phase angle)(>45° of the formulations, which indicates a predominantly viscous behaviour. Still, both formulations can be turned into predominantly elastic (phase angle<45°) by the addition of propylene glycol: Expts. 3.8 & 3.10, phase angles @0.5 Hz 39° & 34° respectively.

TABLE-US-00013 TABLE 4 (figures in % by weight) Example No. 4-1 4-2 4-3 4-4 4-5 I-2 1.20 4.80 9.60 2.40 2.40 SAG 1572 0.10 0.10 0.10 0.10 0.10 DAHP 25.00 25.00 25.00 25.00 25.00 Geropon T36 1.00 0.81 0.81 2.50 0.50 Morwet D-425 1.00 0.81 0.81 2.50 0.50 Antarox B/848 20.00 20.00 20.00 20.00 20.00 Aerosil R812S 4.00 4.00 4.00 4.00 4.00 Propylene Glycol 15.00 15.00 15.00 15.00 15.00 Dipropylene Glycol To To To To To Monomethyl Ether 100% 100% 100% 100% 100% (Dowanol DPM) Dynamic Viscosity 1267/ 2112/ 2415/ 1002/ 631/ @ shear rate 24/s, 500 770 1015 555 334 120/s (mPas) at room temperature G′ @ 0.5 Hz (Pa) 13858 1044 1681 177 249 at room temperature G″ @ 0.5 Hz (Pa) 5218 111 16 249 73 at room temperature Phase Angle @ 21 6 0.5 55 16 0.5 Hz (°) at room temperature

[0476] Evaluation of the Experiments in Table 4:

[0477] The formulations according to the invention can be manufactured with different amounts of active ingredient without losing their satisfactory rheological properties. Indeed, formulation examples 4-1, 4-2, 4-3 all retain elastic rheological properties (Phase angle<30°) while showing shear thinning behaviour. Additionally, the use of high amounts of surfactants is not necessary to control the rheological behaviour of the formulations, as can be seen by the properties of formulation example 4-4, which shows a high phase angle)(>45° due to the high concentration of the dispersants Geropon T-36 and Morwet D-425. As can be seen in Formulation example 4-5, concentrations of surfactants at the 0.5% range are compatible with high elasticity of the formulation (phase angle 16°), and shear thinning behaviour.

EXAMPLE III

[0478] For the purpose of testing the long term stability of the most suitable formulations, suitable thickeners in the presence of suitable dispersing aids as specified in Table 5 are combined and are milled by one of the below mentioned methods: [0479] 1) Formulation components are homogenized with a colloidal mill, and subsequently, milled in a bead mill (Dispermat SL50, 80% 2 mm beads, 4000 rpm, circulation grinding for 40 min). After the time has elapsed, the samples are cooled down to room temperature and the rheological properties of the formulation are assessed. [0480] 2) Formulation components are mixed in a bottle, which is then closed, clamped in an agitator apparatus (Retsch MM301) and treated at 30 Hz for 40 minutes; in the course of this, the samples heat up. After the time has elapsed, the samples are cooled down to room temperature and the rheological properties of the formulation are assessed.

[0481] Subsequently, a storage test is conducted at elevated temperature and then a qualitative/quantitative assessment of appearance, phase separation, rheological properties and dispersion stability after storage (e.g. viscosity), active ingredient concentration is performed

[0482] The assessment of appearance takes place analogously to DIN 10964 “Sensory analysis—Simple descriptive test”. For this purpose, the samples to be examined are examined visually and, if required, by means of shaking and tilting, for shape, state of matter and colour and further peculiarities (especially, for example, lumps, caking, sediment formation, subsequent thickening, marbling of the sediment etc.).

[0483] Phase separation directly after storage is reported either as sediment content and calculated from the quotient H1 [level of the interface layer between sediment phase and supernatant] divided by HO [total fill height of the sample], or as done here by the supernatant content:

Sediment content=(H1/H0)*100[%] or

Supernatant content=100−sediment content[%]

[0484] The rheological properties of the formulation were assessed with a Gemini Rheometer (Bohlin Instruments). The measurement of G′ (elastic modulus), G″ (viscous modulus) and Phase Angle are measured at different frequencies (between 0.01-5 Hz) at room temperature using a frequency sweep routine with ether strain or stress control. The assessment of viscosity is performed at room temperature as per the CIPAC MT192; “Viscosity of Liquids by rotational viscometry” method.

[0485] Dispersion stability in 2% aqueous dilution is determined by analysing the amount of residue deposited after a certain amount of time according to the CIPAC MT 180 Method “Dispersion stability of suspo-emulsions”

TABLE-US-00014 TABLE 5 (figures in % by weight) 5-3 5-4 5-5 (comparative (comparative (comparative Example No. 5-1 5-2 example) example) example) I-2 2.40 2.40 2.40 2.40 2.40 Geropon T36 1.00 1.00 1.00 1.00 1.00 Morwet D-425 1.00 1.00 1.00 1.00 1.00 Antarox B/848 20.00 20.00 20.00 20.00 20.00 DAHP 25.00 25.00 25.00 25.00 25.00 SAG 1572 0.10 0.10 0.10 0.10 0.10 Bentone 34 — — 4.00 — — Bentone 38 — — — 4.00 — Bentone LT — — — — 4.00 Aerosil R812S 4.00 4.00 — — — Propylene Glycol 15.00 10.00 15.00 15.00 15.00 Dipropylene Glycol To 100% To 100% To 100% To 100% To 100% Monomethyl Ether (Dowanol DPM) Appearance of Concentrate Appearance Flowable Flowable Flowable Flowable Flowable Concentrate light brown light brown light brown light brown light brown dispersion dispersion dispersion dispersion dispersion Appearance — — Solid, flows Solid, flows Flowable Concentrate after 2 after shaking after shaking light brown weeks at 54° C. dispersion Appearance Flowable Flowable Solid, flows Very thick Flowable Concentrate after 4 light brown light brown after shaking flowable light brown weeks at room dispersion dispersion dispersion dispersion temperature Appearance Flowable Flowable — — — Concentrate after 4 light brown light brown weeks at 54° C. dispersion dispersion Syneresis/Phase Separation Supernatant after 4 W 97% 98% — — — at 54 [%] Characterization of the Light brown Light brown — — — sediment after storage at 54° C. for 4 W Rehomogenizability Good Good — — — after storage at 54° C. for 4 W Supernatant after 4 W 97% 98% — — — storage at room temperature [%] Characterization of the Light brown Light brown — — — sediment after storage at room temperature for 4 w Rehomogenizability Good Good — — — after storage at room temperature for 4 w Rheological Properties Dynamic viscosity @ 1600 1508 890 1210 406 24 1/s fresh sample [mPa .Math. s] at room temperature Dynamic viscosity @ 597 585 437 (@121 1/s) 531 (@121 1/s) 309 (@121 1/s) 108 1/s fresh sample [mPa .Math. s] at room temperature Dynamic viscosity @ — — 1572 2321 — 24 1/s after 2 W storage @ 54° C. [mPa .Math. s] at room temperature Dynamic viscosity @ — — 689 (@121 1/s) 919 (@121 1/s) — 108 1/s after 2 W storage @ 54° C. [mPa .Math. s] at room temperature Dynamic viscosity @ 363 293 — — — 24 1/s after 4 W storage @ 54° C. [mPa .Math. s] at room temperature Dynamic viscosity @ 276 214 — — — 108 1/s after 4 W storage @ 54° C. [mPa .Math. s] at room temperature Dynamic viscosity @ 505 450 2326 3682 1693 24 1/s after 4 W storage @ room temperature [mPa .Math. s] at room temperature Dynamic viscosity @ 323 293 934 (@121 1/s) 1334 (@121 1/s)  679 (@121 1/s) 108 1/s after 4 W storage @ room temperature [mPa .Math. s] at room temperature G′ @ 0.5 Hz (Pa) at 30 6355 223 178 2.2 room temperature, fresh sample G″ @ 0.5 Hz (Pa) at 468 7387 68 49 3.2 room temperature, fresh sample Phase Angle @ 0.5 Hz 86 49 17 15 55 (°) at room temperature, fresh sample G′ @ 0.5 Hz (Pa) at — — 940 1117 843 room temperature after 2 W storage @ 54° C. G″ @ 0.5 Hz (Pa) at — — 83 94 21 room temperature after 2 W storage @ 54° C. Phase Angle @ 0.5 Hz — — 5 5 1 (°) at room temperature after 4 W storage @ 54° C. G′ @ 0.5 Hz (Pa) at 15 6 — — — room temperature after 4 W storage @ 54° C. G″ @ 0.5 Hz (Pa) at 15 8 — — — room temperature after 4 W storage @ 54° C. Phase Angle @ 0.5 Hz 46 53 — — — (°) at room temperature after 4 W storage @ 54° C. G′ @ 0.5 Hz (Pa) at 155 76 1040 1460 801 room temperature after 4 W storage @ room temperature, fresh sample G″ @ 0.5 Hz (Pa) at 63 50 79 277 27 room temperature after 4 W storage @ room temperature, fresh sample Phase Angle @ 0.5 Hz 22 33 4 11 2 (°) @ room temperature after 4 W storage @ room temperature Dispersion Stability (2% formulation, CIPAC C Water, room temperature) Dispersion stability 0.05 0.05 7 3 1 after 1 h fresh sample [mL] Dispersion stability — — 7 9 3 after 1 h after 2 W storage @ 54° C. [mL] Dispersion stability 0 0.05 — — — after 1 h after 4 W storage @ 54° C. [mL] Dispersion stability 0.1 0.1 8 5 2 after 1 h after 4 W storage @ room temperature [mL]

[0486] Evaluation of the experiments in Table 5:

[0487] Using fillers such as Aerosil R812S and different combination of propylene glycol/dipropylene glycol monomethyl ether it is possible to produce stable formulations having different viscosities (Recipes 5-1, 5-2). Indeed, both recipes are stable during storage and show very good sedimentation stability. After storage of the formulations after 4 weeks at room temperature or at 54° C., the phase separation observed of both examples 5-1 and 5-2 is very small.

[0488] Both examples 5-1 and 5-2 develop during storage at room temperature a considerably more elastic rheological behaviour. This is visible as the initially high phase angle becomes, after 4 weeks at room temperature, substantially smaller)(<35°. An increased elastic rheological behaviour translates in increased sedimentation stability. Particularly beneficial is that example 5-1 behaves more elastic (and thus more stable) than example 5-2 without a proportional viscosity increase.

[0489] A further factor for ascertaining formulation stability is the dispersion stability of the formulation in aqueous dilution. Both examples 5-1, 5-2 are dispersable in water, and after storage at room temperature or at 54° C. in some cases the phase separation of the diluted formulation is relatively small (<=0.1 mL).

[0490] The use of fillers other than the silica based Aerosil R812S leads to formulations with significant disadvantages. This is exemplified with the comparative examples 5-3, 5-4, 5-5 which make use respectively of the organoclay based fillers Bentone 34, Bentone 38, Bentone LT. The use of these organoclay fillers result in the case of 5-3 and 5-4 in formulations with very high viscosities, which increase during storage. The viscosity increase eventually results in the comparative examples 5-3 and 5-4 becoming at some point during storage solid, and only flowable after vigorous shaking.

[0491] Additionally, the dispersion stability behaviour of the comparative examples 5-3, 5-4, 5-5 is significantly worse than that of the examples according to the invention 5-1 and 5-2. Indeed, 1 hour after dispersion in water, the comparative examples have produced a large amount of sediment, whereas the examples according to the invention have barely settled any insoluble material. This an advantage for the examples according to the invention because, for instance, the insoluble residues produced by the comparative examples e.g. can clog application equipment, or negatively affect the bioavailability of the active ingredient.

[0492] In conclusion, the silica fillers (examples according to the invention) and the organoclay fillers (comparative example) have different technical properties, and the examples according to the invention have significant advantages in viscosity and handling, as well as in the usability of the formulation upon dispersion in water. Additionally, the use of fumed silicas lead to stable formulations (very limited phase separation during storage) without the very large viscosity measured for some of the comparative examples. Therefore, the use of silica fillers in the examples according to the invention in Table 5 is an improvement over the comparative examples based on organoclay fillers in Table 5.