IMPROVEMENTS IN OR RELATING TO COPPER BASED PESTICIDES

Abstract

The effect of aqueous compositions of copper based fungicides is improved by including a mixture of sodium dioctyl sulfosuccinate and sodium lauryl sulphate surfactants in the aqueous composition which does not require the presence of a bicarbonate.

Claims

1. A pesticide spray composition comprising an aqueous composition containing: i. 0.010 wt % to 3 wt preferably 0.015 wt % to 3 wt of copper metal derived from a copper salt ii. 0.0025 wt % to 10 wt % of a mixture of sodium dioctyl sulfosuccinate and sodium lauryl sulphate, wherein the mixture is a surfactant mixture; wherein the composition is free of bicarbonate salts, such as potassium and sodium bicarbonate.

2. The pesticide spray composition according to claim 1, in which the ratio of sodium dioctyl sulfosuccinate and sodium lauryl sulphate is from 2:1 to 1:2 parts by weight.

3. The pesticide spray composition according to claim 1 containing from 0.001 wt % to 6 wt % of the surfactant mixture.

4. The pesticide spray composition according to claim 3, containing from 0.01 to 1 wt preferably from 0.02 to 0.4 wt of the surfactant mixture.

5. The pesticide spray composition according to claim 1, wherein the sodium lauryl sulfate present in the preparation is equal to, less than or greater than the an amount of sodium dioctyl sulfosuccinate; the amount being by weight.

6. The pesticide spray composition according to claim 1 wherein the copper metal derived from the copper salt in the formulation is selected from copper sulfate, copper hydroxide, cuprous oxide, copper oxychloride, copper ammonium carbonate, and copper octanoate.

7. (canceled)

8. A pesticide formulation for mixing with water comprising: i. from 5 wt % to 30 wt % of copper metal derived from a copper salt; ii. from 3 wt % to 40 wt % sodium dioctyl sulfosuccinate; and iii. from 3 wt % to 40 wt % sodium lauryl sulfate.

9. (canceled)

10. (canceled)

11. The pesticide spray composition obtained by mixing a formulation according to claim 8 with water to produce a preparation that contains from 0.015% to 3% copper metal derived from a copper salt, preferably 0.05% to 0.3% copper metal derived from a copper salt, more preferably % to 1.5% copper metal together with a surfactant mixture of the sodium dioctyl sulfosuccinate and the sodium lauryl sulfate diluted respectively by the same amounts.

12. A use of a pesticide spray composition according to claim 1 for inhibiting, ameliorating, preventing or treating a plant and/or soil for insect infestation such as treatment for aphids, mites, flies, scales, or thrips.

13. The use according to claim 12 as an insecticide and for the prevention or treatment of aphids on sugar beet.

14. The A use of a pesticide spray composition according to claim 1 for inhibiting, ameliorating, preventing or treating a plant and/or soil for fungal disease such as scab, downy mildew, late blight, Alternaria, Stemphylium, Taphrina, Septoria, and other leaf spot diseases.

15. The use according to claim 14 for the treatment of downy mildew on crop vegetation.

16. The use according to claim 14 in which the crop vegetation comprises hops, fruit, nuts, vegetables and ornamentals.

17. The use according to claim 14 as a fungicide for the prevention or remediation of downy mildew on lettuce.

18. The use according to claim 14 as a fungicide and for the prevention or treatment of Sclerotinia on oilseed rape.

19. The use according to claim 14 as a fungicide and for the prevention or treatment of Cercospora leaf spot on sugar beet.

20. The use according to claim 14 for the treatment of downy mildew on grape vines.

21. A use of the surfactant mixture in a pesticide spray composition according to claim 1 to improve retention and dispersion of the copper compound on vegetation.

22. The use according to claim 21 to reduce the a necessary treatment rate of copper metal to achieve a desired effect.

23. The use according to claim 22 in which the reduction is 40% or more.

Description

[0047] The present invention is illustrated by the following Examples

Example 1

[0048] A formulation (comparative formulation) containing [0049] i. 708 grams per kilo of potassium bicarbonate [0050] ii. 100 grams per kilo of copper hydroxide to provide 65.15 grams per kilo of copper metal [0051] iii. 125 grams per kilo of a 2:1 mixture of sodium dioctyl sulfosuccinate and sodium lauryl sulfate

[0052] was compared with a formulation (inventive) containing [0053] i. 18.0 wt % copper hydroxide to provide 11.7 wt % copper metal [0054] ii. 22.5 wt % of a 2:1 mixture of sodium dioctyl sulfosuccinate and sodium lauryl sulfate

[0055] The copper hydroxide was milled to an average particle size in the range 1 to 5 microns. The formulations were mixed with water to provide an aqueous suspension of copper hydroxide and tested for control of the fungus Sclerotinia sclerotiorum on stems and pods of oilseed rape by spraying onto the oilseed rape 2.5 and 5 litres per hectare of the inventive spray composition and 2.5 and 5 kilograms per hectare of the comparative (bicarbonate containing) preparation each applied in 300 litres water volume per hectare.

[0056] The performance was also compared with a fungicide Efilior from Certis Europe B.V. (133 g/l boscalid+60 g/l metconazole SC).

[0057] The results were as follows.

TABLE-US-00001 PESSEV PESINC PESSEV Yield stems stems pods (Kg/m.sup.2) UTC 25.00a 24.00a 22.50a 5.11 2.5 kg/ha CF 21.25ab 10.75b 13.75bc 5.18 5 kg/ha CF 12.50bc 9.00b 9.75bcd 5.41 2.5 l/ha IF 13.75bc 9.00b 13.75bc 5.56 5 l/ha IF 15.50abc 6.75b 7.75cd 5.71 1 l/ha ref. 4.75c 2.50b 3.75d 5.63 PESSEV = pest severity (%) PESINC = pest incidence (%) UTC = untreated control CF = comparative formulation IF = inventive formulation Ref. (reference fungicide) = Efilior Values followed by same letter or symbol do not significantly differ (P = 0.05 Student-Newman-Keuls)

[0058] Control of Sclerotinia disease on stems with the preparation of the inventive formulation was at least as good as that of the preparation of the comparative formulation, and better on pods than the preparation of the comparative formulation. The yields of rape seed from the crop sprayed with the preparation of the inventive formulation were considerably higher than the yields of the crop sprayed with the preparation of the comparative formulation.

Example 2

[0059] The spray compositions of the inventive formulation and the comparative formulation of Example 1 were applied to sugar beet at respective treat rates of 2.5 and 5 litres and 2.5 and kilograms per hectare to investigate the control of the fungus Cercospora beticola. The crop was evaluated by counting the leaves of the middle crown of 25 plants showing symptoms prior to treatment and 14 days after treatment and after a further 14 days and again after 30 days.

[0060] The results were compared with similar crops treated with the conventional fungicide Amistar Gold from Syngenta (125 g/l azoxystrobin+125 g/l difenoconazole SC) and the results were as follows showing the products of the invention to be superior.

TABLE-US-00002 PESSEV UTC 26.7a 2.5 kg/ha CF 13.1bc 5 kg/ha CF 12.7bc 2.5 l/ha IF 11.4bc 5 l/ha IF 9.0c 1 l/ha ref. 17.6abc PESSEV = pest severity (%) UTC = untreated control CF = comparative formulation IF = inventive formulation Ref. (reference fungicide) = Amistar Gold Values followed by same letter or symbol do not significantly differ (P = 0.05 Student-Newman-Keuls)

[0061] In this trial, the field technician reported a strong infestation of aphids and significant greening effects were observed with the higher dose-rate of the inventive formulation through control of aphids (Myzus persicae and Aphis fabae) which act as vectors for viral and bacterial diseases.

Example 3

[0062] Results of tests with Downy Mildew (Plasmopara viticola) on Grapevine Seedlings Grapevine seedlings were cultivated under controlled environment conditions and treated with Cuprozin Progress by spraying to run-off at the four leaves phenological stage. 24 hours after treatment, foliar discs were placed in Petri-dishes and inoculated with a spore suspension of Plasmopara viticola on the abaxial surface of the leaves. Scoring for disease symptoms was carried out after 6-9 days in a growth chamber (18 ° C., 16 h photoperiod, 60% relative humidity).

[0063] Disease severity was calculated from a quantitative notation scale ranging from 0-100% of sporulation. Cuprozin Progress was applied at 5 and 20 ppm alone or in mixture with adjuvant combination AD-001 at 5-125 ppm as aqueous spray formulations. Statistical analysis was performed to determine if results were significantly different at 95% confidence limit (n=40). Disease incidence was 100% in the untreated control (UTC).

[0064] The results were as follows.

TABLE-US-00003 Disease Efficacy against Treatment Severity (%) Plasmopara viticola (%) Water control (UTC) 76 — 5 ppm Cuprozin Progress 61.7 18.8 20 ppm Cuprozin Progress 50.1 34.1 5 ppm Cuprozin Progress + 56.1 26.2 5 ppm AD-001 5 ppm Cuprozin Progress + 52.3 31.2 20 ppm AD-001 5 ppm Cuprozin Progress + 48.9 35.7 50 ppm AD-001 5 ppm Cuprozin Progress + 40.7 46.5 125 ppm AD-001 20 ppm Cuprozin Progress + 43.6 42.7 5 ppm AD-001 20 ppm Cuprozin Progress + 40.9 46.3 20 ppm AD-001 20 ppm Cuprozin Progress + 39.4 48.1 50 ppm AD-001 20 ppm Cuprozin Progress + 41.7 45.1 125 ppm AD-001 5 ppm AD-001 79.9 −5.1 20 ppm AD-001 75.6 0.5 50 ppm AD-001 63 16.5 125 ppm AD-001 59 22.6

[0065] Cuprozin Progress is a suspension concentrate product obtained from Certis Europe B.V. containing 383 g/l copper hydroxide (28.7% w/w). AD-001 is a combination of two surfactants, sodium lauryl sulphate (SLS) and sodium dioctyl sulfosuccinate (SDS) containing 33.3% (w/w) SLS and 66.7% (w/w) SDS.

[0066] Compatibility analysis using the Colby formula (1967, 2015) demonstrated synergistic or additive effects with the mixture of Cuprozin Progress and adjuvant combination AD-001.

TABLE-US-00004 Expected Observed Type of Treatment Value Value Combination 5 ppm Cuprozin Progress + 14.7% 26.2% Synergistic 5 ppm AD-001 5 ppm Cuprozin Progress + 19.2% 31.2% Synergistic 20 ppm AD-001 5 ppm Cuprozin Progress + 32.2% 35.7% Additive/ 50 ppm AD-001 Synergistic 5 ppm Cuprozin Progress + 37.2% 46.5% Synergistic 125 ppm AD-001 20 ppm Cuprozin Progress + 30.7% 42.7% Synergistic 5 ppm AD-001 20 ppm Cuprozin Progress + 34.4% 46.3% Synergistic 20 ppm AD-001 20 ppm Cuprozin Progress + 45.0% 48.1% Additive/ 50 ppm AD-001 Synergistic 20 ppm Cuprozin Progress + 49.0% 45.1% Additive/ 125 ppm AD-001 Antagonistic

[0067] With both 5 and 20 ppm Cuprozin Progress, synergism or additive effects with AD001 were seen at adjuvant rates of AD001 of 5-50 ppm.

[0068] These results demonstrate the performance of the spray formulations of the invention in relation to powdery mildew on grape vines. Different results would be expected in relation to the treatment of other infections on different vegetation.

Example 4

Results of Tests with Downy Mildew (Bremia lactucae) on Lettuce

[0069] Lettuce seedlings were cultivated under controlled environment conditions and treated with Cuprozin Progress at the first leaf stage. 24 hours after treatment, the seedlings were inoculated with a spore suspension of Bremia lactucae and scored for disease symptoms after 11 days.

[0070] Disease severity was calculated from a quantitative notation scale ranging from 0-100% leaf surface infected with Bremia lactucae sporulation. Statistical analysis was performed to determine if results were significantly different at 95% confidence limit (n=60). Disease incidence was 100% in the untreated control (UTC).

TABLE-US-00005 Disease Efficacy against Significant Severity Bremia lactucae Difference Treatment (%) (%) to UTC Water control (UTC) 88 — — 5 ppm Cuprozin Progress 75 15 no 50 ppm Cuprozin Progress 35 60 yes 100 ppm Cuprozin Progress 14 85 yes 250 ppm Cuprozin Progress 8 92 yes 500 ppm Cuprozin Progress 0 100 yes

[0071] Cuprozin Progress is a suspension concentrate (SC) product from Certis Europe B.V. containing 383 g/l copper hydroxide (28.7% w/w).

[0072] In a second test, Cuprozin Progress was applied at 50 ppm alone or in mixture with adjuvant combination AD-001 at 250 ppm. Disease incidence was 100% in the untreated control (UTC).

TABLE-US-00006 Disease Efficacy against Significant Severity Bremia lactucae Difference Treatment (%) (%) to UTC Water control (UTC) 95 — — 50 ppm Cuprozin Progress 57 40 yes 250 ppm AD-001 91 4 no 50 ppm Cuprozin Progress + 44 54 yes 250 ppm AD-001

[0073] AD-001 is a combination of two surfactants, sodium lauryl sulphate (SLS) and sodium dioctylsulfosuccinate (SDS) containing 33.3% (w/w) SLS and 66.7% (w/w) SDS.

[0074] Compatibility analysis using the Colby formula (1967, 2015) demonstrated synergistic efficacy with the mixture of Cuprozin Progress and adjuvant combination AD-001.

TABLE-US-00007 Expected Observed Type of Treatment Value Value Combination 50 ppm Cuprozin Progress + 43% 54% Synergistic 250 ppm AD-001

Example 5

[0075] The surface wetting and deposition of copper from spray compositions was determined by comparing compositions containing 15 ppm copper hydroxide with varying amounts of sodium lauryl sulfate (Agnique SLS) on its own, varying amounts of sodium dioctyl sulfosuccinate (Geropon SDS) on its own and various mixtures of the two surfactants.

[0076] Contact angles of the same compositions were also measured.

[0077] The measurements were made using a Kruss DSA30 Drop shape analyser.

[0078] The results of the surface tension measurements were as follows.

TABLE-US-00008 Agnique Geropon Agnique SLS:Geropon SLS SDS SDS (1:2) Concentration surface tension (mN/m) (ppm) theoretical actual 5 70.4 70.0 70.1 69.8 20 70.5 55.5 60.5 67.9 50 67.3 49.6 55.4 53.1 125 64.7 47.6 53.2 43.6 250 64.6 43.9 50.7 41.6

[0079] Synergistic behaviour is demonstrated at 125 and 250 ppm rates of combined adjuvants with a significantly lower actual surface tension. This is in-line with microscope observations which revealed the formation of unique structuring around the copper particles at the same rates that there is a rate dependent effect of the combined adjuvants although it also shows that the adjuvancy effect may come into play between 20 and 50 ppm where there is sufficiently low surface tension to provide a degree of wetting along with deposit structuring.

[0080] The contact angle measurements showed a similar trend. Agnique SLS has very little effect on contact angle with values >100° across all rates. For the Geropon SDS compositions, there is a stepwise reduction from 5 ppm onwards. Contact angles for the combination virtually mimic those of Geropon SDS alone showing the strong surface activity of this component. Increasing Geropon SDS concentrations increase wettability and surface coverage of sample droplets.

Example 6

[0081] The interactions between the surfactants and also the interaction between the surfactants and the copper hydroxide were investigated by depositing samples of the spray composition employed in Example 5 onto glass microscope slides and onto a wax surface (purified beeswax), to more closely represent the waxy surface of plant foliage. The spray deposits were allowed to dry and then imaged at 100 times and 400 times magnification.

[0082] It was found that even at the lowest combined adjuvant concentration matrices form within the droplets, and associations with copper hydroxide occur when adjuvant films come into contact.

[0083] With a spray solution containing 15 ppm copper hydroxide, 7 ppm Agnique SLS and 13 ppm Geropon SDS the adjuvant coverage was shown to be widespread, forming connections with copper hydroxide particles when they come into contact. At ×400 magnification intermediary structures incorporating elements of Agnique SLS and Geropon SDS structuring are apparent and the combined adjuvant structuring is more localised around copper hydroxide particles, with clearly defined interactions.

[0084] A spray composition containing 15 ppm copper hydroxide, 42 ppm Agnique SLS and 83 ppm Geropon SDS shows increasing interactions between the adjuvants, leading to reduced total adjuvant coverage within the droplet. More complex, localised, and larger structures are formed, and are more commonly associated with copper hydroxide.

[0085] At the highest combined concentration tested (spray solution 15 ppm copper, 83 ppm Agnique SLS and 167 ppm Geropon SDS) adjuvant associations with copper hydroxide were shown to be complex, with numerous connections. Adjuvant matrices were shown to form indiscriminately, although it is more common for intricate structuring to occur in association with copper hydroxide.

[0086] Accordingly this study has shown a close link between the physical wetting properties of the adjuvant mixtures and the formation of synergistic complex structures.

[0087] Generally, Geropon SDS by itself will often form an indiscrete film, in which copper hydroxide particles can become entrapped. Conversely, Agnique SLS appears to closely associate with copper hydroxide particles via crystal seeding, using the copper hydroxide as a substrate.

[0088] Imperfections on the wax surface seem to promote greater crystal seeding and structuring from the adjuvants at the lower concentrations, when compared with images on glass surfaces. The observed behaviour is very consistent between glass and wax surfaces. The effect of the combined surfactant system has been shown to create a more mobile, interconnected system, entrapping and closely associating with copper particles. It further shows that increased wettability from the higher rates of Geropon SDS leads to increased probability of interactions between Agnique SLS and copper hydroxide, resulting in more widespread and effective structuring.

[0089] Higher concentrations have been shown to lead to synergistic interactions between the adjuvants leading to fewer discrete areas of coverage and instead larger, more complex, and localised structures are formed around the copper. This appears to correlate with the trend in reducing surface tension and contact angle producing better wetting of the surface, facilitating mobility of the adjuvants and the formation of complex structures. The existence of these unique macrostructures is believed to enhance the field performance of the spray solutions of this invention because of the concentration effect of adjuvants and the formation of a flexible, highly associated copper containing network across the surface.