USE OF HYDROPHOBIC, SELF-EMULSIFYING POLYGLYCEROL ESTERS AS ADJUVANTS AND ANTI-SPRAY-DRIFT AGENT

Abstract

Compositions comprising at least one hydrophobic, at least partially water-insoluble polyglycerol ester in combination with at least one emulsifier, and the use thereof.

Claims

1-10. (canceled)

11. A composition, comprising: at least one hydrophobic, at least partially water-insoluble polyglycerol ester in combination with at least one emulsifier.

12. The composition according to claim 11, wherein the polyglycerol ester has an HLB value of 8 or less.

13. The composition according to claim 11, comprising a polyglycerol ester of the Formula 2
M.sub.aD.sub.bT.sub.c  Formula 2 wherein M=[C.sub.3H.sub.5(OR).sub.2O.sub.1/2], D=[C.sub.3H.sub.5(OR).sub.1O.sub.2/2], T=[C.sub.3H.sub.5O.sub.3/2], a.sup.=1 to 10, b=0 to 10, c=0 to 3, wherein, the sum total of a+b+c is 1 to 20, wherein the radicals R independently of one another are identical or different radicals of the formula R′—C(O)— or H, wherein R′ is a monovalent aliphatic, saturated or unsaturated hydrocarbon radical having 3 to 39 C atoms, wherein at least one radical R corresponds to a radical of the formula R′—C(O)—.

14. The composition according to claim 12, wherein the polyglycerol ester has an HLB of from 4 to 6.5 and has the Formula 2 and has an arithmetic mean of 2.9 to 3.1 radicals R of the formula R′—C(O)—, wherein the acyl radicals are fatty acid mixtures comprising oleic acid, stearic acid, palmitic acid and gamma-linolenic acid, wherein oleic acid, stearic acid, palmitic acid and gamma-linolenic acid amount to at least 85% by weight in the fatty acid mixture.

15. The composition according to claim 11, comprising an emulsifier with an HLB of 9 or greater.

16. The composition according to claim 15, comprising at least one sorbitan fatty acid ester as emulsifier.

17. An additive for a crop protection formulation, comprising: the composition according to claim 11.

18. A method for avoiding spray drift, comprising: adding the additive of claim 17 to a crop protection formulation.

19. A method for enhancing the efficacy of a pesticide and simultaneously for avoiding spray drift, comprising: adding the additive of claim 17 to a crop protection formulation.

20. A method for enhancing the efficacy of a pesticide, simultaneously for avoiding spray drift and for increasing the yield of an agricultural crop, comprising: adding the additive of claim 17 to a crop protection formulation.

Description

EXAMPLES

General Methods and Materials:

Substances:

[0086] In the experiments which follow, a mixture of 80% by weight of triglyceryl trioleate with 20% by weight of polyethylene glycol—20 sorbitan trioleate was used and diluted with water.

Spraying Experiments:

[0087] All spraying experiments were carried out using a flat-spray nozzle of the type XR 11003 from TeeJet. All the spraying experiments were carried out here at a spraying pressure of 1 bar. The droplet size of the resulting spray was determined by image analysis of highly resolved images of the spray. To this end, a high-speed camera of the type Vision Research Phantom V12 was positioned perpendicularly to the spray lamella 12 cm below the nozzle exit, and the spray was filmed for 20 sec at a magnification of 1.15 for at least 20 seconds. The droplet size distribution was subsequently determined by image analysis of at least 2000 independent static individual images of the spray. To this end, the individual drops were detected on the basis of their intensity deviating from the background. The projected area of each drop was then determined from the recorded images, which was used to calculate an equivalent diameter: D=(4*A/pi).sup.0.5, where D is the equivalent diameter and A is the projected area. The result obtained was a volume-weighted droplet size distribution, by means of which the maximum of the distribution and the mean volumetric diameter (MVD) can be determined. This image analysis was carried out here using the computer program Matlab (for details and background, see, for example, R. C. Gonzalez, S. L. Eddins and R. E. Wood, “Digital Image Processing using Matlab”, 2004, Prentice Hall Verlag, or see K. J. Hay, Z.-C.-Liu, T. J. Hanratty, “A Backlighted Imaging Technique for Particle Size Measurements in Two Phase Flows”, Experiments in Fluids, 1998, 25(3), 226-232).

Determination of the Particle Size in Emulsions:

[0088] The particle size in emulsions was determined by laser diffraction measurements using the Malvern MasterSizer 3000. The measurements were carried out here in dilute aqueous solutions. The evaluation of the scattered signal was carried out automatically by the software supplied with the instrument. The result obtained was a volume-weighted particle size distribution. In order to ensure that the droplet size of the emulsion does not change as a result of diluting, an estimation of the droplet size was additionally carried out by viewing micrographs of the undiluted emulsion.

Comparative Example 1: Spraying Experiment with Pure Water

[0089] Fully-demineralized water was atomized under the above-described conditions. FIG. 1 shows the volume-weighted droplet size distribution determined with the help of image analysis.

[0090] The maximum of the droplet size distribution is at 260 μm. Moreover, a mean volumetric diameter of 252 μm will be determined.

Example 2 According to the Invention: Spraying Experiment with Water+Polyglycerol Ester

[0091] With gentle stirring, 0.1 parts by weight of the composition according to the invention was incorporated into 99.8 parts by weight of water. The emulsion of the defoamer active-substance mixture obtained had a droplet size of less than 100 μm (determined by laser diffraction using a Malvern MasterSizer 3000). This mixture was atomized under the experimental conditions stated hereinabove. FIG. 2 shows the volume-weighted droplet size distribution determined with the aid of high-speed video recordings.

[0092] The maximum of the droplet size distribution in comparison with fully-demineralized water shifted from 260 μm to 340 μm. The MVD shifted from 252 μm for pure water to 351 μm as a result of the anti-drift additive (FIG. 2).

Example 3: Biological Activity

[0093] Field trials were designed in which crop plants, for example cereal species (barley and wheat), legume (soya) and the fibre plant cotton, were treated with crop protection agents (CPA) in order to protect them against diseases or to control insects. Likewise, field trials were designed in which broad-leaved weeds and grass weeds were treated with a nonselective herbicide (damages all green plants) or with selective herbicides (controls only the weed, but is not harmful for the crop plant). The application of these substances which are generally referred to as “crop protectants” was carried out either after dilution with water alone or mixed in the same spray tank with different doses of the adjuvants according to the invention. The application was carried out at points in time at which such products are conventionally applied by spraying in order to protect crop plants or to control weeds.

TABLE-US-00001 TABLE X Crop protection agents used in Examples 3.1 to 3.7: Pesticides (component of active Code Trade name substances) Manufacturer CPA-1 Amistar Opti 250 g/l azoxystrobin + Syngenta, 500 g/l Basel chlorothalonil Switzerland CPA-2 Capalo 75 g/l metrafenone + BASF, 62.5 g/l Ludwigshafen, epoxyconazole + Germany 200 g/l fenpropimorph CPA-3 Seguris 125 g/l isopyrazam + Syngenta, 90 g/l Basel epoxyconazole Switzerland CPA-4 Score 250 g/l Syngenta, difenoconazole Basel Switzerland CPA-5 Actara 250 g/kg Syngenta, thiamethoxam Basel Switzerland CPA-6 Cato Komp. A + 250 g/kg rimsulfuron + DuPont, Germany Banvel 4S 480 g/l dicamba Stähler Suisse SA, Zofingen, Switzerland CPA-7 Roundup 450 g/l glyphosate Monsanto, USA salt

[0094] The active substances belong to the following classes of chemical active substances, which are thereby represented: [0095] strobilurins: azoxystrobin, pyraclostrobin [0096] carboxamides: isopyrazam [0097] triazoles: epoxyconazole, difenoconazole [0098] benzophenones: metrafenone [0099] morpholins: fenpropimorph [0100] neonicotinoids: thiamethoxam [0101] sulphonylureas: rimsulphoron [0102] growth regulators: dicamba [0103] nonselective herbicide: glyphosate

TABLE-US-00002 TABLE XX Identity of the adjuvants as used: Code Adjuvant Composition ADJ-1 Adjuvant according to the 80% polyglycerol ester + invention 20% emulsifier ADJ-2 Commercial adjuvant, not Organo-modified according to the trisiloxane, BREAK-THRU invention S240 (Evonik Industries AG, Essen, Germany)

General Description of the Field Trials:

[0104] The design of field trials for testing fungicides in cereal species or legume species is known in principle to the skilled worker. The same applies to the design of trials for testing insecticides in cotton and for testing nonselective herbicides (a nonselective herbicide is one that kills all plants, including crop plant, when the plants come into contact with it) and selective herbicides (do not kill the crop plant when they come into contact with the agent, but kill the undesired broad-leaved plant or grass which is to be eliminated) in maize and other crop plants. Therefore, the procedure will only be described in summary here:

[0105] In fields with uniformly grown cereals (barley, wheat), legumes (soybeans), cotton and maize, plots of 10 to 37 m.sup.2 in size were distributed randomly in four replicated blocks with four replications. The grass species Brachiaria plantaginea and Digitaria horizontalis and the broad-leaf weed Acanthospermum hispidum were sown in plots for the trials with the nonselective herbicide CPA-8.

[0106] The plants in the four plots of each treatment remained untreated or were treated with crop protection agents (see Table X) alone or in combination with adjuvants (see Table XX). The test products were diluted with water (use composition) and applied to the plants by means of a flat-spray nozzle, preferably an AI nozzle, in a water volume of 150 to 300 l/ha. In some case, the spray treatment was repeated at an interval of 2 to 4 weeks.

[0107] The result of the treatment was determined on different days after spraying the plants, using a representative number of plants per plot. The disease level in the untreated control was likewise scored. The results of the treatment are given in the examples as the mean of the 4 plots which were sprayed separately in each experiment.

[0108] The disease symptoms caused by fungal attack is given as the total of the areas diseased with one and/or more diseases (in % of the leaf area). A lower percentage in a comparison is therefore a positive result.

[0109] In the experiments with insect attack, 10 leaves were sampled from each plot on different days after the spray treatment. The number of insects was counted. The lower the number, the higher the activity of the agents. In the herbicide experiments, the activity of the spray treatment was scored in such a way that the biomass production of the treated plots (m*) was related to the biomass production in the untreated plots (m.sup.0), and the activity was calculated using the formula

efficacy=1−(m*/m.sup.0)

[0110] Here, an activity of 100% is attained when all of the biomass in the treated plot has been killed, and 0% activity when no effect whatsoever on the biomass by the treatment has been found. A higher percentage in a comparison is therefore a positive result.

[0111] At the point in time of the cereals' and the legume's kernel maturity, the plots of each treatment were harvested, and the kernel weights were weighed for each plot. The moisture of the kernels was determined, and the yields were calculated for each plot for a specific uniform fresh weight (in the case of cereals, 14% moisture; in the case of legumes (soybean) 9% moisture) so as to compensate for irregularities in the fresh weight between the individual plots. Thereafter, the kernel weight was extrapolated to a uniform area of one hectare in size. A higher yield in a comparison is therefore a positive result.

[0112] The infection with the plant pathogens (fungi and insects) was not induced, but originated from the environment.

Example 3.1: Winter Barley

[0113] In a field with winter barley cv. “Tenor” at growth stage 41 (all leaves fully developed), the CPA-1 and the adjuvants ADJ-1 and ADJ-2 were diluted in 200 l/ha water and the mixture was sprayed onto the plants.

[0114] Before the application, the plants were infected with powdery mildew (caused by the pathogenic fungus Blumeria graminis) and by ramularia (caused by the pathogenic fungus Ramularia collo-cygni). The disease symptoms of the leaves were determined on the second leaf below the flag leaf, 14 days after the application. The grain yields were determined after the crop had been harvested. The application rates of the products and the results are shown in Table A.

TABLE-US-00003 TABLE A Disease symptoms of the leaves, and grain yield as per Example 3.1: Disease symptoms, Disease symptoms, Grain powdery mildew ramularia yield Treatment [%] (%) [dt/ha] Untreated 15 17.5 47.4 1.5 l/ha CPA-1 8.5 16.3 58.6 1.5 l/ha CPA-1 + 6.0 9.0 64.0 0.25 l/ha ADJ-1 1.5 l/ha CPA-1 + 1.5 5.0 65.2 0.5 l/ha ADJ-1 1.5 l/ha CPA-1 + 2.0 11.8 63.9 0.2 l/ha ADJ-2

[0115] The results demonstrate that the fungicide alone reduced the disease symptoms. The combination of the fungicide with the composition according to the invention, and the comparative adjuvant, showed a marked increase. A higher dosage of the ADJ-1 had a higher activity, as expected, with the higher dosage exceeding the activity of the comparison. The grain yields increased in the same manner.

Example 3.2: Winter Wheat

[0116] In a field with winter wheat cv. “Akteur” at growth stage 32 (2-node stage) and again at growth stage 51 (all leaves fully developed, beginning of ear emergence), the CPA-2 and the adjuvants ADJ-1 and ADJ-2 were diluted with 200 l/ha water and the mixture was sprayed onto the plants. Before the application, the plants were infected by septoria leaf spot (caused by the pathogenic fungus Mycosphaerella graminicola). The disease symptoms were determined 27 days after the first application and 26 days after the second application, on the first leaf below the flag leaf. The grain yields were determined after the crop had been harvested. The application rates of the products and the results are shown in Table B.

TABLE-US-00004 TABLE B Disease symptoms of the leaves, and grain yield as per Example 3.2: Disease symptoms, Disease symptoms, Grain first determination second determination yield Treatment [%] (%) [dt/ha] Untreated 14.0 91.3 81.8 1 l/ha CPA-2 7.5 22.8 93.1 1 l/ha CPA-2 + 4.5 17.9 96.5 0.25 l/ha ADJ-1 1 l/ha CPA-2 + 4.3 17.7 96.6 0.5 l/ha ADJ-1 1 l/ha CPA-2 + 6.3 16.5 92.7 0.2 l/ha ADJ-2

[0117] The results demonstrate that the fungicide alone reduced the disease symptoms on both scoring dates and increased the grain yield over the untreated control. Both adjuvants tested improved the activity of the fungicide in winter wheat. Only the application of the fungicide together with the composition according to the invention resulted in a further yield increase. The success of the application of the composition according to the invention appears to be dose-independent.

Example 3.3: Winter Wheat

[0118] In a field with winter wheat cv. “Genius” at growth stage 49 (all leaves fully developed), the CPA-3 and the adjuvants ADJ-1 and ADJ-2 were diluted with 200 l/ha water and the mixture was sprayed onto the plants. Before the application, the plants were infected by septoria leaf spot (caused by the pathogenic fungus Mycosphaerella graminicola). The disease symptoms were determined 37 days after the application on the first leaf underneath the flag leaf and on the flag leaf. The application rates of the products and the results are shown in Table C.

TABLE-US-00005 TABLE C Disease symptom of the leaves as per Example 3.3: Disease symptoms, Disease symptoms, leaf underneath flag leaf flag leaf Treatment [%] (%) Untreated 8.8 48.8 0.75 l/ha CPA-3 3.4 26.7 0.75 l/ha CPA-3 + 3.3 20.3 0.5 l/ha ADJ-1 0.75 l/ha CPA-3 + 2.6 18.5 0.2 l/ha ADJ-2

[0119] The results show that the fungicide alone reduced the disease symptoms on both leaves studied. Both test adjuvants improved the activity of the fungicide in winter wheat further, especially on the leaf underneath the flag leaf.

Example 3.4: Soybean

[0120] In a field with soybeans cv. “Potencia” at growth stage R3 (beginning pod), the CPA-4 and the adjuvants ADJ-1 and ADJ-2 were diluted with 150 l/ha water and the mixture was sprayed onto the plants. Before the application, the plants were infected by rust disease (caused by the pathogenic fungus Phakopsora pachyrhizi). The disease symptoms were determined 14 and 28 days after the application, on the lower leaves of the plants. The application rates of the agents and the results are shown in Table D.

TABLE-US-00006 TABLE D Disease symptoms of the leaves and grain yield as per Example 3.4: Disease symptoms, Disease symptoms, 14 days 28 days Treatment [%] (%) Untreated 11.7 42.7 0.1 l/ha CPA-4 8.4 34.1 0.1 l/ha CPA-4 + 4.9 20.3 0.2 l/ha ADJ-1 0.1 l/ha CPA-4 + 4.5 16.0 0.4 l/ha ADJ-1 0.1 l/ha CPA-4 + 4.6 22.1 0.2 l/ha ADJ-2

[0121] The results show that the fungicide alone reduced the disease symptoms on the soybean plants in comparison with the untreated control. Both test activity adjuvants improved the efficacy of the fungicide.

Example 3.5: Cotton

[0122] In a field with cotton plants cv. “Fiber Max” at beginning of anthesis (flowers unopened, plants are approximately 70 cm in height), the CPA-5 and the adjuvants ADJ-1 and ADJ-2 were diluted with 150 l/ha water and the mixture was sprayed onto the plants. After the spray coating had dried on (approximately 1 hour after the application), half of the treated plots were sprayed from a nozzle with approximately 8 mm/m.sup.2 water so as to simulate rain. The purpose was to determine whether the rain simulation washed off the crop protection agent and whether this would result in a reduced activity against the insects. The number of aphids (Aphidae) was counted on 10 leaves per plot 7 days after the application and is shown in Table E and the application rates of the agents are stated.

TABLE-US-00007 TABLE E Number of aphids per leaf as per Example 3.5, in parentheses % of untreated: After rain Treatment Without rain simulation Untreated 18.8 (100) 13.1 (100) 0.1 kg/ha CPA-5 10.7 (57)  9.8 (75) 0.1 kg/ha CPA-5 + 9.1 (48) 7.5 (57) 0.2 l/ha ADJ-1 0.1 kg/ha CPA-5 + 7.2 (38) 6.5 (50) 0.4 l/ha ADJ-1 0.1 kg/ha CPA-5 + 9.8 (52) 7.1 (54) 0.2 l/ha ADJ-2

[0123] The results demonstrate that the application of the insecticide alone reduced the number of aphids. Obviously, some of the insecticide was washed off by rain unless combined with an adjuvant. Both adjuvants increased the activity of the insecticide, in particular the ADJ-1 at the higher dosage. In relative terms, the ADJ-1 increased the rainfastness of the insecticide to a similar extent as the commercial ADJ-2.

Example 3.6: Weeds in Crops

[0124] In a field with maize at growth stage 16 (6 leaves developed), cv. “Falkone”, in plots in which the grass weed Echinochloa crus-galli (approx. 10 plants per m.sup.2, with 2-3 leaves per plant) and also the broad-leaved weed Chenopodium album (approx. 10 plants/m.sup.2, likewise with 2-3 leaves) occurred, the CPA-6 alone or together with the adjuvants ADJ-1 or ADJ-2 was diluted with 200 l/ha water and the mixture was sprayed onto the plants. The CPA-6 consists of two components, rimsulfuron, which preferentially inhibits the growth of grasses, and dicamba, which controls broad-leaved weeds. Both agents are selective in maize, which means that the herbicide does not damage maize. The occurrence of two target weeds was scored 52 days after the plants had been sprayed, and the activity of the treatment was scored in relation to the plants' growth in the untreated control. The degree of weed cover of the control area was 32%, and the degree of cover of the treatment area was 39%. The data in Table F express the efficacy of the treatment. The application rates of the agents and the results are shown in Table F.

TABLE-US-00008 TABLE F Efficacies (%) of the treatment on the grass Echinochloa crus-galli and the broad-leaved weed Chenopodium album as per Example 3.6: Efficacy Efficacy against against grass broad-leaved weeds Treatment [%] [%] CPA-6 (0.025 kg Cato + 0.25 l 55 65 Banvel 4S)/ha, CPA-6 (0.025 kg Cato + 0.25 l 94 95 Banvel 4S)/ha) + 0.25 l/ha ADJ-1 CPA-6 (0.025 kg Cato + 0.25 l 97 94 Banvel 4S)/ha) + 0.5 l/ha ADJ-1 CPA-6 (0.025 kg Cato + 0.25 l 91 94 Banvel 4S)/ha) + 0.2 l/ha ADJ-2

[0125] The results show that both adjuvants increase the efficacies of the herbicide combination to above 90%, while the herbicides alone only exerted a weak activity. The activity of the composition according to the invention appears to be dose-independent.

Example 3.7: Weed without Crop, Nonselective Herbicide

[0126] B. decumbens and G. horizontalis and also A. hispidum were sown in a field. When the plants had reached a growth height of 30-35 cm (B. decumbens) and 35-40 cm (D. horizontalis) and 50-60 cm (A. hispidum) respectively, they were treated with CPA-7 alone or in diluted form together with adjuvants ADJ-1 or ADJ-2 with 150 l/ha of water. The CPA-7, as is known, is not very rainfast, i.e. if rain falls shortly after the application, the activity is greatly reduced because agents are washed off the plants by the rain. To improve the rainfastness, one may resort to adjuvants. For this reason, the plots were designed in duplicate (with the respective 4 replications), and 1 hour after the application 8 mm/m.sup.2 of water was sprayed over a period of 10 minutes, using a nozzle, so as to simulate rain. The activity of the applications was scored 30 days after the application. The data in Table G show the degree of efficacy of the treatment. The application rates of the agents and the results are shown in Table G.

TABLE-US-00009 TABLE G Degrees of efficacy (%) of the treatment on the grasses Brachiaria decumbens (a) and Digitaria horizontalis (b), and on the broad- leaved plant Acanthospermum hispidum (c), without rain and after simulated rain post-application as per Example 3.7. Efficacy Efficacy after without rain rain (simulated) Treatment [%] [%] (a) 0.75 l/ha CPA-7 79 61 0.75 l/ha CPA-7 + 89 74 0.2 l/ha ADJ-1 0.75 l/ha CPA-7 + 96 79 0.4 l/ha ADJ-1 0.75 l/ha CPA-7 + 85 70 0.2 l/ha ADJ-2 (b) 0.75 l/ha CPA-7 89 74 0.75 l/ha CPA-7 + 94 81 0.2 l/ha ADJ-1 0.75 l/ha CPA-7 + 98 84 0.4 l/ha ADJ-1 0.75 l/ha CPA-7 + 95 73 0.2 l/ha ADJ-2 (c) 0.75 l/ha CPA-7 81 80 0.75 l/ha CPA-7 + 98 89 0.2 l/ha ADJ-1 0.75 l/ha CPA-7 + 100 94 0.4 l/ha ADJ-1 0.75 l/ha CPA-7 + 96 76 0.2 l/ha ADJ-2

[0127] The results show that both adjuvants increased the efficacies of the nonselective herbicide. The composition according to the invention increased the activity of the nonselective herbicide after rain better than the commercial ADJ-2, in particular at the higher application rate.