WO2010020477A2 - Crop safeners - Google Patents

Crop safeners Download PDF

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Publication number
WO2010020477A2
WO2010020477A2 PCT/EP2009/058799 EP2009058799W WO2010020477A2 WO 2010020477 A2 WO2010020477 A2 WO 2010020477A2 EP 2009058799 W EP2009058799 W EP 2009058799W WO 2010020477 A2 WO2010020477 A2 WO 2010020477A2
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WO
WIPO (PCT)
Prior art keywords
crop
neocryl
mowilith
diafenthiuron
safener
Prior art date
Application number
PCT/EP2009/058799
Other languages
French (fr)
Other versions
WO2010020477A3 (en
Inventor
Max Angst
Sherif Ayoub
Stefan Baum
Peter Burri
Patrick Joseph Mulqueen
David Stock
Johanna Martina Williams
Original Assignee
Syngenta Participations Ag
Syngenta Limited
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Application filed by Syngenta Participations Ag, Syngenta Limited filed Critical Syngenta Participations Ag
Priority to EA201100357A priority Critical patent/EA018318B1/en
Priority to CN2009801326867A priority patent/CN102131391B/en
Priority to AU2009284353A priority patent/AU2009284353A1/en
Priority to JP2011523366A priority patent/JP5502866B2/en
Priority to BRPI0917522-9A priority patent/BRPI0917522A2/en
Publication of WO2010020477A2 publication Critical patent/WO2010020477A2/en
Publication of WO2010020477A3 publication Critical patent/WO2010020477A3/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl

Definitions

  • the invention relates to the novel use as crop safeners, of a group of polymeric chemicals and in particular their use to reduce and/or prevent the phytotoxicity of insecticidal compositions comprising diafenthiuron on crops of useful plants.
  • the invention thus includes novel insecticidal compositions comprising diafenthiuron and a crop safener, and to the use of such compositions in controlling insects in crops of useful plants.
  • the invention further extends to combination packages of diafenthiuron and crop safener. When employed at recommended rates and dilutions, the insecticide diafenthiuron ⁇ 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea; entry No.
  • the invention provides an insecticidal composition comprising diafenthiuron and a crop safener.
  • the present invention is based on the unexpected finding that certain polymeric chemical compounds are capable of ameliorating phytotoxicity caused by diafenthiuron.
  • the polymeric compounds may suitably be vinyl acetate polymers or copolymers; acrylic polymers or copolymers; or polyethers.
  • Suitable polymeric chemical compounds for use in the invention include (but are not limited to) Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and lndtron which are commercially available materials as follows: Atlox Semkote E-135 (available from Croda) is an ethylene vinyl acetate copolymer.
  • NeoCryl A-2099 available from DSM NeoResins
  • NeoCryl A-1120 (available from DSM NeoResins) is an acrylic-styrene copolymer.
  • NeoCryl A-615 (available from DSM NeoResins) is an acrylic copolymer.
  • Mowilith LDM2418 (available from Celanese) is a vinyl acetate and VeoVa® (vinyl ester of versatic acid) copolymer.
  • Mowilith DHF 57S (available from Celanese) is a vinyl acetate homopolymer.
  • TEXICRYL 17-0422 (available from Scott Bader) is an acrylic polymer.
  • Vinamul 18160 (available from Celanese) is a vinyl acetate polymer.
  • Sandovit (available from Syngenta India) is an alkyl-aryl-polyglycolether.
  • lndtron available from lndofil Chemicals Company is an alkyl phenoxy polyethoxyethanol.
  • NeoCryl A2099 is used in overprint varnishes and barrier coating
  • NeoCryl A-615 is used in clear wood finishes and plastic coatings.
  • Sandovit and lndtron are manufactured as surfactants for use in agrochemical formulations
  • Vinamul 18160 has been used in fungicide formulations
  • none of the above-mentioned group of chemicals has been used as either (i) a crop safener or (ii) in combination with diafenthiuron previously.
  • compositions comprising diafenthiuron ameliorate the phytotoxic effects that are observed when diafenthiuron is applied to crops as an insect control agent, in particular when such adjuvants are present at low concentrations (typically 2% v/v or less) in such applications.
  • concentrations typically 2% v/v or less
  • the invention provides a method of reducing or preventing phytotoxicity in crops of useful plants, wherein said phytotoxicity is caused by the application of diafenthiuron to said crop of useful plants, said method comprising applying diafenthiuron in combination with a crop safener selected from the group consisting of Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and lndtron, to said crop of useful plants.
  • the phytotoxic effect on plants may be assessed visually as a function of the percentage of reddening to the leaves and/or the appearance of necrosis.
  • Crop safeners for use in the invention are typically polymeric chemicals and will typically reduce the phytotoxicity to 10% or less reddening of leaves in comparison to untreated plants.
  • Preferred polymeric chemicals for use in the invention will typically reduce the phytotoxicity to 7% or less, whilst the most preferred polymeric chemicals will typically reduce phytotoxicity to 5% or less.
  • the above values are approximate as any purely visual assessment is likely to contain a degree of subjectivity. Diafenthiuron for use in the invention may be obtained as described in US
  • the crop safener that is employed according to the invention is typically selected from the group consisting of Atlox Semkote E-135
  • NeoCryl A-2099 available from Croda
  • NeoCrylA-1 120 available from NeoCryl A615 (all available from DSM NeoResins) Mowilith LDM 2418, Mowilith DHF 57S (both available from Celanese)
  • TEXICRYL 17-0422 available from Scott Bader
  • Vinamul 18160 (Celanese)
  • Sandovit available from Syngenta India
  • lndtron available from lndofil Chemicals Company.
  • the skilled man will be aware of, and appreciate that alternative, chemically similar adjuvants may also be employed to the same effect in the invention.
  • the polymeric chemicals/ adjuvants that are used as crop safeners have a minimum film forming temperature of less than 30 0 C, more preferably 20 0 C or less, and a solubility in water of 1% or less.
  • Each component of an insecticidal composition of the invention may be used in unmodified form, i.e. as obtainable from synthesis. However, each may be formulated (either separately or together) in any suitable manner using standard formulation adjuvants, such as carriers, solvents and surface-active substances, for example, as described hereinafter. Such formulations can be in the form of concentrates which are diluted prior to use, although ready-to-use formulations can also be made. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the invention provides an insecticidal formulation comprising (i) diafenthiuron, (ii) a crop safener as described herein, and (iii) a standard formulation adjuvant.
  • diafenthiuron is formulated with a standard formulation adjuvant, and subsequently combined with the crop safener (which may be formulated, or as obtained from synthesis) prior to spraying.
  • the diafenthiuron, crop safener and standard formulation adjuvant will all be formulated together.
  • Formulations of the invention can be in various physical forms, e.g.
  • diafenthiuron is formulated as a wettable powder or as a suspension concentrate, and the crop safener will be in unmodified form or formulated as a liquid.
  • diafenthiuron, crop safener and standard formulation adjuvant will be formulated as a wettable powder or as a suspension concentrate.
  • the formulations may be prepared e.g. by mixing diafenthiuron and/or the crop safener with the standard formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • Further standard formulation adjuvants such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof, may also be included in formulations of the invention.
  • Standard formulation adjuvants that are suitable for the preparation of formulations according to the invention are known per se.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2- butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, di
  • Water is generally the carrier of choice for diluting the concentrates.
  • suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001.
  • a large number of surface-active substances may advantageously be used in the formulations, especially in those formulations designed to be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate;
  • Further standard formulation adjuvants that can usually be used in the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers.
  • Formulations of the invention may additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10%, based on the spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rh ⁇ ne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred additive contains, for example, as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of C 8-22 fatty acids, especially the methyl derivatives of C 12 - 1 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-11 1-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112- 62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000. Another preferred adjuvant is Adigor® (Syngenta AG) which is a methylated rapeseed oil-based adjuvant.
  • the application and action of the oil additives may be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO97/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C 12 - 22 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • Examples of commercially available surfactants are the Genapol types (Clariant AG).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of the surface-active substances in relation to the total additive is generally from 1 to 30% by weight.
  • oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).
  • an organic solvent may contribute to an additional enhancement of action.
  • Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80% by weight of the total weight.
  • Oil additives that are present in admixture with solvents are described, for example, in US- A-4,834,908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation).
  • a further oil additive that is preferred according to the invention is SCORE®(Syngenta Crop Protection Canada).
  • it is also possible for formulations of alkylpyrrolidones e.g.
  • Agrimax® to be added to the spray mixture.
  • Formulations of synthetic lattices e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.
  • the diafenthiuron component and the crop safener component may be manufactured and/or formulated separately and subsequently combined prior to spraying (for example upon dilution as a "tank mix", as employed in the Examples hereinafter).
  • each of these components may be packaged in combination.
  • a further aspect of the invention provides combination pack of insecticide and crop safener, said pack comprising a first container containing diafenthiuron and a second container containing a crop safener.
  • lnsecticidal compositions and formulations according to the invention may be used to control insects, phytopathogenic mites and/or ticks, on crops of useful plants.
  • a method of controlling insects on a crop of useful plants comprising applying to said insects, or said crop, or the location of said insects or said crop, an insecticidal composition or insecticidal formulation as described herein.
  • compositions and formulations find utility against sucking insects, mites and whitefly, and more specifically against Tetranychidae (especially Tetranychus urticae), Aphids (especially Aphis gossypii) and whitefly (especially Bemisia tabaci).
  • Crops of useful plants in which compositions and formulations of the invention may used to control insects, and/or in which phytotoxicity may be reduced or prevented, include cotton and vegetables.
  • Preferably said crop is a cotton crop.
  • Crops is to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering, as well as those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt cotton (resistant to cotton boll weevil e.g. NuCOTIN33B® (cotton), Bollgard® (cotton). Any suitable method of application may be employed to effect application of compositions or formulations of the invention to crops of useful plants, insects, or the location of insects/crop plants. These include large and small spray application methods (e.g. spray application via boom bar, spray from knapsack with single/triple nozzle etc.) with which the skilled man will be familiar.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors
  • Bt cotton resistant to cotton boll wee
  • diafenthiuron will be applied at a rate of between 250 g active ingredient per hectare (g ai/Ha) and 80Og ai/Ha, for example at 250, 300, 400 or 80Og ai/Ha, in a spray volume of from 150L/Ha to 500 L/Ha (e.g. 150 UHa, 200 UHa, 250UHa, 300 UHa).
  • Crop safener will be included to give a concentration of from 0.02% v/v to 2% v/v.
  • crop safener will be applied at the following concentrations 0.07% v/v, 0.1 % v/v, 0.25% v/v or 1 % v/v.
  • Cotton (cultivar CIM-496) BBCH72 and treated with compositions comprising diafenthiuron in the form of POLO® 500 SC at a rate of 250g/ha, either alone or in combination with Atlox Semkote E-135.
  • Two applications to the crop were made, separated by a one week interval. Applications were made in either a high (H) spray volume (700 L/ha) or low (L) spray volume (200L/ha) using a single nozzle knapsack sprayer.
  • Compositions comprising Atlox Semkote E-135 contained this component at a concentration of 0.03% v/v.
  • the degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves at 4 and 7 days after application (NB. 7 day assessment for first spray was carried out prior to second spray), in comparison to untreated cotton. The results are shown in Table 1 below. Table 1
  • Cotton (Vishal-1 1 ) was grown to BBCH73 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified.
  • diafenthiuron formulated either as WP or SC and applied at the rates as indicated.
  • One application to the crop was made using a knapsack sprayer with a triple cone nozzle and a spray volume of 700 L/Ha.
  • the degree of phytotoxicity was assessed as a function of the percentage of reddening (% Red.) to cotton leaves at 4, 7 and 10 days after application, in comparison to untreated cotton. Necrosis (if observed) was also noted. The results are shown below in Table 2.
  • Cotton (Vishal-11 was grown to stage BBCH73 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton. Assessments were carried out at 4 and 7 days after application 1 (NB. 7 day assessment for first spray was carried out prior to second spray), and at 4, 7 and 10 days after application 2. The results are shown in Table 3 below.
  • Cotton (Vishal-11 was grown to stage BBCH72 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton. Assessments were carried out at 4 and 7 days after each application (NB. 7 day assessment for first spray was carried out prior to second spray). The results are shown below in Table 4.
  • Cotton (Vishal-11 ) was grown to stage BBCH72 and treated with diafenthiuron WP50 at a rate of 300g/Ha, either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton (control data). Assessments were carried out at 4 and 7 days after each application (NB. 7 day assessment for first spray was carried out prior to second spray). The results are shown in Table 5 below.
  • a non-replicated single plot (100m 2 ) filed trial was carried out to assess the effect of various polymeric chemicals - Atlox Semkote E-135 "Atlox” (Croda), NeoCryl A-2099 “2099” (DSM NeoResins), and N eoCryl A-1 120 "1 120" (DSM NeoResins) - on diafenthiuron-mediated phytotoxicty in transgenic cotton.
  • Bt-cotton (Vishal-1 1 ) was grown for 90 days to stage BBCH72 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified.
  • Cotton (cultivar Delta Opal) was grown to stage BBCH67 and then sprayed with diafenthiuron (formulated either as WP or SC and applied at 80Og ai/Ha) either alone, or in combination with the test chemicals at the concentrations specified. Foliar application to the crop was effected by boom bar with six cone nozzles (3 nozzles per row), using a spray volume of 150 L/Ha. The results are shown below in Tables 7 and 8. The degree of phytotoxicity was assessed as a function of the percentage of reddening (% Red.) to cotton leaves at either 6, 8 and 1 1 days after application (trial 1 , Table 7) or 6, 8 and 12 days after application (trial 2, Table 8). Necrosis was assessed qualitatively, with + indicating some slight necrosis, ++ a greater degree of necrosis and +++ indicating substantial necrosis.

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Abstract

The invention relates to the novel use as crop safeners, of a group of polymeric chemicals, and in particular their use to reduce and/or prevent the phytotoxicity of insecticidal compositions comprising diafenthiuron on crops of useful plants. The invention thus includes novel insecticidal compositions comprising diafenthiuron and a crop safener, and to the use of such compositions in controlling insects in crops of useful plants. The invention further extends to combination packages of diafenthiuron and crop safener.

Description

CROP SAFENERS
The invention relates to the novel use as crop safeners, of a group of polymeric chemicals and in particular their use to reduce and/or prevent the phytotoxicity of insecticidal compositions comprising diafenthiuron on crops of useful plants. The invention thus includes novel insecticidal compositions comprising diafenthiuron and a crop safener, and to the use of such compositions in controlling insects in crops of useful plants. The invention further extends to combination packages of diafenthiuron and crop safener. When employed at recommended rates and dilutions, the insecticide diafenthiuron {1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea; entry No. 229 The Pesticide Manual 14th Edition, 2006, Ed. C D S Tomlin, Pub. BCPC} effectively controls a wide spectrum of insect pests without any appreciable damage to the crop to which it is applied. However there have been reports that under certain climatic conditions and/or use regimes diafenthiuron can cause reddening of leaves and/or necrotic spots. It is therefore desirable to find methods of avoiding these potential problems. As an example with the increasing prevalence for the growth of genetically modified cotton, in particular in dryer climates and where local farming practise involves using small spray volumes and single nozzle application of pesticides, this unexpected problem of phytotoxicity needs to be addressed in order to provide the farmer with a broader armoury against cotton insect pests that are not typically controlled through the GM route or traditional insect control measures.
Thus according to a first aspect, the invention provides an insecticidal composition comprising diafenthiuron and a crop safener.
The present invention is based on the unexpected finding that certain polymeric chemical compounds are capable of ameliorating phytotoxicity caused by diafenthiuron. In particular the polymeric compounds may suitably be vinyl acetate polymers or copolymers; acrylic polymers or copolymers; or polyethers. Examples of suitable polymeric chemical compounds for use in the invention include (but are not limited to) Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and lndtron which are commercially available materials as follows: Atlox Semkote E-135 (available from Croda) is an ethylene vinyl acetate copolymer. NeoCryl A-2099 (available from DSM NeoResins) is an acrylic-styrene copolymer.
NeoCryl A-1120 (available from DSM NeoResins) is an acrylic-styrene copolymer. NeoCryl A-615 (available from DSM NeoResins) is an acrylic copolymer. Mowilith LDM2418 (available from Celanese) is a vinyl acetate and VeoVa® (vinyl ester of versatic acid) copolymer.
Mowilith DHF 57S (available from Celanese) is a vinyl acetate homopolymer. TEXICRYL 17-0422 (available from Scott Bader) is an acrylic polymer. Vinamul 18160 (available from Celanese) is a vinyl acetate polymer.
Sandovit (available from Syngenta India) is an alkyl-aryl-polyglycolether. lndtron (available from lndofil Chemicals Company) is an alkyl phenoxy polyethoxyethanol.
These polymeric chemical compounds typically find utility as adjuvants in a broad range of industries, for example NeoCryl A2099 is used in overprint varnishes and barrier coating and NeoCryl A-615 is used in clear wood finishes and plastic coatings. Whilst Sandovit and lndtron are manufactured as surfactants for use in agrochemical formulations, and Vinamul 18160 has been used in fungicide formulations, none of the above-mentioned group of chemicals has been used as either (i) a crop safener or (ii) in combination with diafenthiuron previously. It is thus extremely surprising that the inclusion of these adjuvants in compositions comprising diafenthiuron ameliorate the phytotoxic effects that are observed when diafenthiuron is applied to crops as an insect control agent, in particular when such adjuvants are present at low concentrations (typically 2% v/v or less) in such applications. The use of an adjuvant to reduce the phytotoxicity of diafenthiuron thus forms a further aspect of the invention.
In yet another aspect, the invention provides a method of reducing or preventing phytotoxicity in crops of useful plants, wherein said phytotoxicity is caused by the application of diafenthiuron to said crop of useful plants, said method comprising applying diafenthiuron in combination with a crop safener selected from the group consisting of Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and lndtron, to said crop of useful plants. The phytotoxic effect on plants may be assessed visually as a function of the percentage of reddening to the leaves and/or the appearance of necrosis. Crop safeners for use in the invention are typically polymeric chemicals and will typically reduce the phytotoxicity to 10% or less reddening of leaves in comparison to untreated plants. Preferred polymeric chemicals for use in the invention will typically reduce the phytotoxicity to 7% or less, whilst the most preferred polymeric chemicals will typically reduce phytotoxicity to 5% or less. The above values are approximate as any purely visual assessment is likely to contain a degree of subjectivity. Diafenthiuron for use in the invention may be obtained as described in US
4328247 or, it may be obtained as a commercial product (e.g. as POLO® 50 WP, POLO® 500SC or PEGASUS®; available from Syngenta Crop Protection AG Basel).
As mentioned hereinbefore, the crop safener that is employed according to the invention is typically selected from the group consisting of Atlox Semkote E-135
(available from Croda), NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615 (all available from DSM NeoResins) Mowilith LDM 2418, Mowilith DHF 57S (both available from Celanese) TEXICRYL 17-0422 (available from Scott Bader), Vinamul 18160 (Celanese), Sandovit (available from Syngenta India) and lndtron (available from lndofil Chemicals Company). The skilled man will be aware of, and appreciate that alternative, chemically similar adjuvants may also be employed to the same effect in the invention. Preferably the polymeric chemicals/ adjuvants that are used as crop safeners have a minimum film forming temperature of less than 300C, more preferably 200C or less, and a solubility in water of 1% or less. Each component of an insecticidal composition of the invention may be used in unmodified form, i.e. as obtainable from synthesis. However, each may be formulated (either separately or together) in any suitable manner using standard formulation adjuvants, such as carriers, solvents and surface-active substances, for example, as described hereinafter. Such formulations can be in the form of concentrates which are diluted prior to use, although ready-to-use formulations can also be made. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
Thus in a further aspect the invention provides an insecticidal formulation comprising (i) diafenthiuron, (ii) a crop safener as described herein, and (iii) a standard formulation adjuvant. In one embodiment of this aspect, diafenthiuron is formulated with a standard formulation adjuvant, and subsequently combined with the crop safener (which may be formulated, or as obtained from synthesis) prior to spraying. In a further embodiment, the diafenthiuron, crop safener and standard formulation adjuvant will all be formulated together. Formulations of the invention can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo- emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. In certain embodiments, diafenthiuron is formulated as a wettable powder or as a suspension concentrate, and the crop safener will be in unmodified form or formulated as a liquid. In further embodiments diafenthiuron, crop safener and standard formulation adjuvant will be formulated as a wettable powder or as a suspension concentrate. The formulations may be prepared e.g. by mixing diafenthiuron and/or the crop safener with the standard formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. Further standard formulation adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof, may also be included in formulations of the invention.
Standard formulation adjuvants that are suitable for the preparation of formulations according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2- butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma- butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octa- decanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d). A large number of surface-active substances may advantageously be used in the formulations, especially in those formulations designed to be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.
Further standard formulation adjuvants that can usually be used in the invention include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilisers.
Formulations of the invention may additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhόne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C8-22 fatty acids, especially the methyl derivatives of C12-18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-11 1-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112- 62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000. Another preferred adjuvant is Adigor® (Syngenta AG) which is a methylated rapeseed oil-based adjuvant.
The application and action of the oil additives may be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30% by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).
If desired, it is also possible for the above-mentioned surface-active substances to be used in formulations of the invention on their own, that is to say without oil additives.
Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80% by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US- A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE®(Syngenta Crop Protection Canada). In addition to the oil additives listed above, it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.
As mentioned hereinbefore, the diafenthiuron component and the crop safener component may be manufactured and/or formulated separately and subsequently combined prior to spraying (for example upon dilution as a "tank mix", as employed in the Examples hereinafter).
In the latter case, each of these components (preferably with diafenthiuron being formulated) may be packaged in combination. Thus a further aspect of the invention provides combination pack of insecticide and crop safener, said pack comprising a first container containing diafenthiuron and a second container containing a crop safener. lnsecticidal compositions and formulations according to the invention may be used to control insects, phytopathogenic mites and/or ticks, on crops of useful plants. Thus in a further aspect of the invention there is provided a method of controlling insects on a crop of useful plants comprising applying to said insects, or said crop, or the location of said insects or said crop, an insecticidal composition or insecticidal formulation as described herein.
Insects, phytopathogenic mites and ticks which may be controlled , for example of the order Lepidoptera, Coleoptera, Homoptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, in crops of useful plants. In particular said compositions and formulations find utility against sucking insects, mites and whitefly, and more specifically against Tetranychidae (especially Tetranychus urticae), Aphids (especially Aphis gossypii) and whitefly (especially Bemisia tabaci).
Crops of useful plants in which compositions and formulations of the invention may used to control insects, and/or in which phytotoxicity may be reduced or prevented, include cotton and vegetables. Preferably said crop is a cotton crop.
The term "Crops" is to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering, as well as those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt cotton (resistant to cotton boll weevil e.g. NuCOTIN33B® (cotton), Bollgard® (cotton). Any suitable method of application may be employed to effect application of compositions or formulations of the invention to crops of useful plants, insects, or the location of insects/crop plants. These include large and small spray application methods (e.g. spray application via boom bar, spray from knapsack with single/triple nozzle etc.) with which the skilled man will be familiar.
Typically diafenthiuron will be applied at a rate of between 250 g active ingredient per hectare (g ai/Ha) and 80Og ai/Ha, for example at 250, 300, 400 or 80Og ai/Ha, in a spray volume of from 150L/Ha to 500 L/Ha (e.g. 150 UHa, 200 UHa, 250UHa, 300 UHa). Crop safener will be included to give a concentration of from 0.02% v/v to 2% v/v. Preferably crop safener will be applied at the following concentrations 0.07% v/v, 0.1 % v/v, 0.25% v/v or 1 % v/v.
Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention. For the avoidance of doubt, literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference
EXAMPLES
Example 1. Effect of Atlox Semkote E-135 on observed phytotoxicty of diafenthiuron in non-transenic cotton
A field trial with three replicated plots (50m2 each ) was carried out to assess the effect of the polymeric chemical Atlox Semokote E-135, and spray volume on the diafenthiuron mediated phytotoxicity in cotton.
Cotton (cultivar CIM-496) BBCH72 and treated with compositions comprising diafenthiuron in the form of POLO® 500 SC at a rate of 250g/ha, either alone or in combination with Atlox Semkote E-135. Two applications to the crop were made, separated by a one week interval. Applications were made in either a high (H) spray volume (700 L/ha) or low (L) spray volume (200L/ha) using a single nozzle knapsack sprayer. Compositions comprising Atlox Semkote E-135 contained this component at a concentration of 0.03% v/v. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves at 4 and 7 days after application (NB. 7 day assessment for first spray was carried out prior to second spray), in comparison to untreated cotton. The results are shown in Table 1 below. Table 1
Figure imgf000010_0001
It can be seen that the lower the spray volume, the greater the degree of diafenthiuron mediated phytotoxicity is observed. The inclusion of Atlox Semkote E-135 at 0.03% reduces the observed phytotoxicity.
Example 2 Effect of Atlox Semkote E-135 and Vinamul 16180 on observed phytotoxicty of diafenthiuron in transgenic cotton at BBCH 73
Two, single plot (200m2) non-replicated field trials were carried out to assess the effect of the polymeric chemicals, Atlox Semkote E-135 ("Atlox", Croda) and Vinamul
16180 ("Vinamul", Celanese) on the phytotoxicity caused by diafenthiuron in transgenic cotton. The first field trial was carried out using a high spray volume, whilst the second was carried out using a low spray volume.
2.1 Trial 1 - Spray volume 700L/Ha
Cotton (Vishal-1 1 ) was grown to BBCH73 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. One application to the crop was made using a knapsack sprayer with a triple cone nozzle and a spray volume of 700 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening (% Red.) to cotton leaves at 4, 7 and 10 days after application, in comparison to untreated cotton. Necrosis (if observed) was also noted. The results are shown below in Table 2.
2.2 Trial 2 - Spray volume 300 L/Ha
Cotton (Vishal-11 was grown to stage BBCH73 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton. Assessments were carried out at 4 and 7 days after application 1 (NB. 7 day assessment for first spray was carried out prior to second spray), and at 4, 7 and 10 days after application 2. The results are shown in Table 3 below.
Figure imgf000011_0001
* no value obtained, faulty application
Example 3 Effect of Atlox Semkote E-135, Sandovit, and lndtron on observed phytotoxicty of diafenthiuron in transgenic cotton
Two, single plot (200m2) non-replicated field trials were carried out to assess the effect of the polymeric chemicals, Atlox Semkote E-135 ("Atlox", Croda), Sandovit (Syngenta India), and lndtron (Indofil Chemicals Company) on the phytotoxicity caused by diafenthiuron in transgenic cotton.
3.1 Trial 1
Cotton (Vishal-11 was grown to stage BBCH72 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton. Assessments were carried out at 4 and 7 days after each application (NB. 7 day assessment for first spray was carried out prior to second spray). The results are shown below in Table 4.
Figure imgf000012_0001
3.2 Trial 2
Cotton (Vishal-11 ) was grown to stage BBCH72 and treated with diafenthiuron WP50 at a rate of 300g/Ha, either alone, or in combination with the test chemicals at the concentrations specified. Two applications to the crop were made, separated by a one week interval, using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening to cotton leaves in comparison to untreated cotton (control data). Assessments were carried out at 4 and 7 days after each application (NB. 7 day assessment for first spray was carried out prior to second spray). The results are shown in Table 5 below.
Figure imgf000013_0001
Example 4 Effect of different polymeric chemicals on observed phytotoxicty of diafenthiuron in transgenic cotton
A non-replicated single plot (100m2) filed trial was carried out to assess the effect of various polymeric chemicals - Atlox Semkote E-135 "Atlox" (Croda), NeoCryl A-2099 "2099" (DSM NeoResins), and N eoCryl A-1 120 "1 120" (DSM NeoResins) - on diafenthiuron-mediated phytotoxicty in transgenic cotton. Bt-cotton (Vishal-1 1 ) was grown for 90 days to stage BBCH72 and treated with diafenthiuron (formulated either as WP or SC and applied at the rates as indicated) either alone, or in combination with the test chemicals at the concentrations specified. One application to the crop was made using a single nozzle knapsack sprayer and a spray volume of 300 L/Ha. The degree of phytotoxicity was assessed as a function of the percentage of reddening (% Red.) to cotton leaves at 6, 8 and 12 days after application. Necrosis (if observed) was also noted. The results are shown below in Table 6.
Figure imgf000013_0002
Figure imgf000014_0001
* (+) = <5% necrosis, ++ >10%
The data shows that all three polymeric chemicals may be used to ameliorate the phytotoxic effects of diafenthiuron.
Example 5 Effect of different polymeric chemicals on observed phytotoxicty of diafenthiuron in non-transgenic cotton
Two non-replicated single plot (60m2) filed trials were carried out to assess the effect of various polymeric chemicals on diafenthiuron-mediated phytotoxicty in non- transgenic cotton. The first trial was carried out to assess the effects of Atlox Semkote E-135 "Atlox" (Croda), Mowilith DHF 57S "57S" (Celanese), Mowilith LDM 2418 "2418" (Celanese), and A-2099 "2099" (DSM NeoResins). The second trial was carried out to assess the effects of Atlox Semkote E-135 "Atlox" (Croda), NeoCryl A-1 120 "1 120" (DSM NeoResins), NeoCryl A-615 "615" (DSM NeoResins), and TEXICRYL 17-0422 "17-0422" (Scott Bader).
Cotton (cultivar Delta Opal) was grown to stage BBCH67 and then sprayed with diafenthiuron (formulated either as WP or SC and applied at 80Og ai/Ha) either alone, or in combination with the test chemicals at the concentrations specified. Foliar application to the crop was effected by boom bar with six cone nozzles (3 nozzles per row), using a spray volume of 150 L/Ha. The results are shown below in Tables 7 and 8. The degree of phytotoxicity was assessed as a function of the percentage of reddening (% Red.) to cotton leaves at either 6, 8 and 1 1 days after application (trial 1 , Table 7) or 6, 8 and 12 days after application (trial 2, Table 8). Necrosis was assessed qualitatively, with + indicating some slight necrosis, ++ a greater degree of necrosis and +++ indicating substantial necrosis.
Figure imgf000014_0002
Figure imgf000015_0001
The data shows that all four chemicals tested ameliorated the phytotoxic effects of diafenthiuron, with Atlox Semkote E-135 and NeoCryl A-2099 being particularly effective.
Figure imgf000015_0002
The data shows that all four chemicals tested ameliorated the phytotoxic effects of diafenthiuron, with Atlox Semkote E-135 and NeoCryl A-1 120 being particularly effective.

Claims

1. An insecticidal composition comprising diafenthiuron and a crop safener.
2. An insecticidal composition according to claim 1 wherein the crop safener is a polymeric material.
3. An insecticidal composition according to claim 2 wherein said crop safener has a minimum film forming temperature of 300C or less and a solubility in water of 1% or less.
4. An insecticidal composition according to claim 3, wherein said crop safener has a minimum film forming temperature of 200C or less.
5. An insecticidal composition according to claim 2 wherein the polymeric material is a vinyl acetate polymer or copolymer.
6. An insecticidal composition according to claim 2 wherein the polymeric material is an acrylic polymer or copolymer.
7. An insecticidal composition according to claim 2 wherein the polymeric material is a polyether.
8. An insecticidal composition according to claim 2, wherein said crop safener is selected from the group of compounds consisting of: Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron.
9. An insecticidal composition comprising (i) diafenthiuron, (ii) a crop safener selected from the group consisting of: Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron; and (iii) a standard formulation adjuvant.
10. A combination pack of insecticide and crop safener comprising a first containiner containing diafenthiuron and a second container containing a crop safener.
1 1. A combination pack according to claim 10, wherein said crop safener is selected from: Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron.
12. A method of controlling insects on crops of useful plants comprising applying to said insects, or said crop, or the location of said insects or said crop, an insecticidal composition as defined in any one of claims 1 to 9.
13. A method of reducing or preventing phytotoxicity in crops of useful plants, wherein said phytotoxicity is caused by the application of diafenthiuron to said crop of useful plants, said method comprising applying diafenthiuron in combination with a crop safener selected from the group consisting of Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1120, NeoCryl A615, Mowilith
LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron, to said crop of useful plants.
14. Use of an adjuvant to reduce the phytotoxicity of diafenthiuron.
15. Use of an adjuvant according to claim 14, wherein said adjuvant is selected from the group consisting of: Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron.
16. Use of a compound selected from the group consisting of: Atlox Semkote E-135, NeoCryl A-2099, NeoCrylA-1 120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, Vinamul 18160, Sandovit, and Indtron, as a crop safener.
17. Use of a compound, selected from the group consisting of: NeoCryl A-2099, NeoCrylA-1120, NeoCryl A615, Mowilith LDM2418, Mowilith DHF 57S, TEXICRYL 17-0422, in an agrochemical formulation.
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CN102905531A (en) * 2010-04-27 2013-01-30 先正达参股股份有限公司 Methods of controlling neonicotinoid resistant aphids
WO2013135617A1 (en) 2012-03-16 2013-09-19 Syngenta Participations Ag Methods and compositions for pest management

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CL2011000357A1 (en) 2011-09-02
UY32068A (en) 2010-03-26
CN102131391B (en) 2013-09-11
MY178707A (en) 2020-10-20
JP2012500239A (en) 2012-01-05
KR20110049807A (en) 2011-05-12
JP5502866B2 (en) 2014-05-28
EA018318B1 (en) 2013-07-30
WO2010020477A3 (en) 2010-09-16
AR073085A1 (en) 2010-10-13
CN102131391A (en) 2011-07-20

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